Polymer and process for producing polymer

ABSTRACT

The object of the present invention is to provide a polymer best suited for use as a medical adhesive excellent in wet adhesion strength (water-resistant adhesive strength). In the present invention, a polymer capable of forming a cured film and useful as a medical adhesive, which has a viscosity at 37° C. of 0.5 to 2,000 Pa·s and shows a saturated water absorption of 0.2 to 5 ml/g, is used. The above-mentioned polymer preferably shows an initial water absorption rate of 0.01 to 0.5 ml/g·min, the wet elongation percentage of the cured film is preferably 100 to 1,500%, and the wet 100% modulus of the cured film is preferably 0.01 to 10 MPa. Additionally, it is preferable that the above-mentioned polymer contains oxyethylene groups and in which the oxyethylene group content is 30 to 100% by weight based on the weight of the polymer.

TECHNICAL FIELD

The present invention relates to a polymer and a process for producingpolymers. More particularly, it relates to a polymer best suited for useas a medical adhesive excellent in water-resistant adhesive strengthwhich is effective in adhesion of wet vital organs such as lung, arteryand heart, in particular, and to a process for producing such a polymer.

BACKGROUND ART

Hydrophilic urethane prepolymers obtainable by reacting afluorine-containing polyisocyanate with a hydrophilic polyether polyolare known in the art as medical adhesives (Japanese Kokai PublicationHei-01-227762).

However, such prior art medical adhesives have problems; namely,heterogeneous reactions may occur due to the high reactivity between thefluorine-containing isocyanate component and hydrophilic polyetherpolyol, resulting in abnormal increases in viscosity during prepolymerpreparation, heterogeneity in prepolymer, and fluctuations in adhesivestrength. Furthermore, there is a problem that such prepolymers have lowwet adhesive strength.

SUMMARY OF THE INVENTION

Thus, it is an object of the present invention to provide a polymer bestsuited for use as a medical adhesive excellent in wet adhesion strength(water-resistant adhesive strength).

The present inventors made intensive investigations in an attempt toaccomplish the above object and found that when a polymer having aspecific level of viscosity and a specific initial water absorption rateis used, a medical adhesive excellent in wet adhesion strength can beobtained. This and further findings have now led to completion of thepresent invention.

Thus, the polymer of the invention is characterized in that it is

a polymer capable of forming a cured film and useful as a medicaladhesive,

which has a viscosity at 37° C. of 0.5 to 2,000 Pa·s and shows asaturated water absorption of 0.2 to 5 ml/g.

DETAILED DESCRIPTION OF THE INVENTION

The viscosity (in Pa·s) at 37° C. of the polymer of the invention ispreferably not lower than 0.5, more preferably not lower than 1,particularly preferably not lower than 3, most preferably not lower than5, and it is preferably not higher than 2,000, more preferably nothigher than 1,000, particularly preferably not higher than 500, mostpreferably not higher than 50. Within such range, the adhesiveapplicability tends to become good.

<Polymer Viscosity Measurement Method>

Viscosity measurements are made using a DA viscometer according to themethod D described in the “Method of testing for viscosity of liquidresins using a rotational viscometer” prescribed in JIS K 7117-1987.Useful as the rotational viscometer is Tokimec INC's model BH viscometerand the like.

The saturated water absorption (in ml/g) of the polymer of the inventionis preferably not smaller than 0.2, more preferably not smaller than0.3, particularly preferably not smaller than 0.4, most preferably notsmaller than 0.5, and preferably not larger than 5, more preferably notlarger than 3, particularly preferably not larger than 1, mostpreferably not larger than 0.7. Within such range, the adhesive strength(in particular initial adhesive strength) tends to become higher.

<Saturated Water Absorption Measurement Method>

Using-an apparatus for D/W method of testing for water absorption rates(buret capacity: 25 ml, length: 55 cm, small opening diameter: 2 mm) asshown in JIS K 7224-1996 “Method of testing for water absorption ratesof highly water absorbing resins”—Illustration 1, measurements arecarried out in a room at 25° C. and 50% humidity with a filter paperhaving a diameter of 3.7 cm (e.g. Whatman's glass microfiber filterGF/A, and the like) installed in lieu of the nonwoven fabric, togetherwith a polycarbonate cylinder having an inside diameter of 3.7 cm.First, with each valve closed, 25 ml of a test solution (physiologicalsaline) is placed in the buret and, then, each valve is opened to fillthe space from the buret to the valves with the test solution. Then, arubber stopper is mounted, the valve below the buret is opened, theoverflowing test solution is wiped off, and the graduation (al) on theburet is read. Then, 1.0 g of the polymer is added onto the filter paperin the cylinder and a ventil with a diameter of 3.7 cm is pushed intothe cylinder for uniform setting of the polymer. After 30 minutes, thegraduation (a2) on the buret is read. The value obtained by subtracting(al) from (a2) is recorded as the saturated water absorption (ml/g).

The initial water absorption rate (in ml/g·min) is preferably not lowerthan 0.01, more preferably not lower than 0.02, particularly preferablynot lower than 0.03, most preferably not lower than 0.04, and preferablynot higher than 0.5, more preferably not higher than 0.3, particularlypreferably not higher than 0.2, most preferably not higher than 0.1.Within such range, the adhesive strength (in particular initial adhesivestrength) becomes higher.

<Initial Water Absorption Rate Measurement Method>

In the same manner as in the saturated water absorption measurement, thegraduation (a3) on the buret is read at 2 minutes after polymer setting,and one half of the value obtained by subtracting (al) from (a3) isrecorded as the initial water absorption rate (ml/g·min).

The cured film of the polymer of the invention preferably has a wetelongation percentage (in %) of not lower than 100, more preferably notlower than 200, particularly preferably not lower than 300, mostpreferably not lower than 400, and preferably not higher than 1,500,more preferably not higher than 1,200, particularly preferably nothigher than 1,000, most preferably not higher than 800. Within suchrange, the adhesive strength (in particular water-resistant adhesivestrength) becomes higher.

Furthermore, the cured film preferably has a wet 100% modulus (in MPa)of not lower than 0.01, more preferably not lower than 0.05,particularly preferably not lower than 0.1, most preferably not lowerthan 0.4, and preferably not higher than 10, more preferably not higherthan 5, particularly preferably not higher than 2, most preferably nothigher than 0.7. Within such range, the adhesive strength (in particularwater-resistant adhesive strength) becomes higher.

<Measurement Method for Wet Elongation Percentage and Wet 100% Modulusof Cured Films>

Cured film test specimens for wet elongation percentage and wet 100%modulus measurements are prepared by applying the polymer on a glassplate to a size of 10 cm square and a thickness of about 100 μm using anapplicator, allowing the coating to stand at 25° C. and 50% RH for 48hours for attaining curing, allowing the same to stand in aphysiological saline bath at 25° C. and, after 24 hours, taking out thesame, and stamping specimens out of the same using a No. 3dumbbell-shaped die described in JIS K 6251-1993. The specimens stampedout are kept in physiological saline for 1 hour, deprived of moisturewith gauze, precisely measured for thickness and, within 5 minutes,subjected to measurements for tensile tensions corresponding toelongation at break and 100% elongation at a rate of pulling of 300mm/min in an atmosphere of 25° C. and 50% RH according to JIS K6251-1993. Employable as the tensile testing machine is such a testingmachine as prescribed in JIS K 6850-1999 (e.g. Shimadzu Corp's modelAGS-500B autograph or the like), or the like.

In accordance with the present invention, the polymer capable of formingcured films includes reactive functional group-containing polymers[polyethers, polyesters, polyamides, polyureas, polyurethanes and vinylpolymers (acrylic polymers, polystyrene, polyolefins, polydienes,natural rubbers, etc.)], and the like. As the reactive functional group,there may be mentioned an isocyanato group, epoxy group (e.g. aglycidyl, 2,3-oxacyclohexyl and the like group), (meth)acryloyl group,cyano(meth)acryloyl group, alkoxysilyl group (e.g. trimethoxysilyl,triethoxysilyl and the like group) and the like group, and precursors ofthese [blocked isocyanato groups (e.g. phenyloxycarbamoyl group) etc.],and the like.

Preferably, the polymer of the invention has a number average molecularweight (Mn) of not lower than 500, more preferably not lower than 800,particularly preferably not lower than 1,000, most preferably not lowerthan 1,200, but not higher than 500,000, more preferably not higher than100,000, particularly preferably not higher than 10,000, most preferablynot higher than 5,000. Within this range, the adhesive strength (inparticular wet adhesive strength) becomes higher. The Mn can bedetermined by gel permeation chromatography (GPC) using polyethyleneglycol species, polystyrene species or the like, as standard substances.

From the adhesive strength (in particular initial adhesive strength) andthe like viewpoint, the polymer of the invention is preferably ahydrophilic polymer. The term “hydrophilic polymer” means a polymerhaving a polyoxyethylene group content of not lower than 30% by weightper molecule or one comparable in affinity for water thereto. Theoxyethylene group content (in % by weight) in the polymer as based onthe polymer weight is preferably not lower than 30, more preferably notlower than 40, particularly preferably not lower than 45, mostpreferably not lower than 50, and preferably not higher than 100, morepreferably not higher than 90, particularly preferably not higher than80, most preferably not higher than 75. Within such range, the adhesivestrength (in particular initial adhesive strength) of the polymerbecomes higher.

From the reactivity and the like viewpoint, the polymer of the inventionis preferably an isocyanato group-containing polymer having isocyanatogroup as a reactive functional group. In cases where the polymer is anisocyanato group-containing one, the isocyanato group content (in % byweight) in the polymer as based on the polymer weight is preferably notlower than 0.1, more preferably not lower than 0.5, particularlypreferably not lower than 1, most preferably not lower than 2, andpreferably not higher than 20, more preferably not higher than 15,particularly preferably not higher than 10, most preferably not higherthan 5. Within such range, the adhesive strength (in particular initialadhesive strength and water-resistant adhesive strength) of the polymerbecomes higher. For isocyanato group content determination, the polymeris dissolved in a solution of an excess amine (e.g. dibutylamine or thelike) in a solvent (e.g. toluene, dimethylformamide, dimethyl sulfoxideor the like) for reaction with the amine, the unreacted portion of theamine is titrated with hydrochloric acid in methanol, and thethus-obtained number of moles of the isocyanato group per unit weight ismultiplied by 42. The product is recorded as the isocyanato groupcontent (% by weight) per unit weight.

The isocyanato group-containing polymer includes urethane prepolymers(UPs) having a structure resulting from the reaction of a polyisocyanate(A) with an active hydrogen-containing polymer (B),non-polyisocyanate-based polymers (NUPs) having a structure resultingfrom conversion of one or more functional groups in an activehydrogen-containing polymer (B) to isocyanato groups, and the like.

Employable as the polyisocyanate (A) to be used in obtaining theurethane prepolymers (UPs) are aromatic polyisocyanates containing 6 to19 carbon atoms (excluding the carbon atoms in the NCO groups;hereinafter the same shall apply), aliphatic polyisocyanates containing1 to 22 carbon atoms, alicyclic polyisocyanates containing 6 to 19carbon atoms, araliphatic polyisocyanates containing 8 to 16 carbonatoms, modifications thereof, mixtures of two or more of these, and thelike.

As the aromatic polyisocyanates, there may be mentioned 1,3- or1,4-phenylene diisocyanate (PDI), 2,4- or 2,6-tolylene diisocyanate(TDI), crude TDI, 2,4′- or 4,4′-diphenylmethanediisocyanate (MDI), crudeMDI, 1,5-naphthalenediisocyanate, 4,4′,4″-triphenylmethanetriisocyanate,m- or p-isocyanatophenylsulfonyl isocyanate, mixtures of these, and thelike.

Employable as the aliphatic polyisocyanates are fluorine-free aliphaticpolyisocyanates, fluorine-containing aliphatic polyisocyanates and thelike.

As the fluorine-free aliphatic polyisocyanates, there may be mentionedmethylene diisocyanate, ethylene diisocyanate, tetramethylenediusocyanate, hexamethylene diisocyanate (HDI), dodecamethylenediisocyanate, 1,6,11-undecanetriisocyanate, 2,2,4-trimethylhexamethylenediisocyanate, lysinediisocyanate, 2,6-diisocyanato methyl caproate,bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate,2-isocyanatoethyl 2,6-diisocyanatohexanoate, mixtures of these, and thelike.

As the fluorine-containing aliphatic polyisocyanates, there may bementioned those represented by OCN—R_(f)—NCO, those represented byOCN—CH₂—R_(f)—CH₂—NCO, those represented by OCN—CF₂—R—CF₂—NCO, thoserepresented by OCN—CH₂—CF₂—R—CF₂—CH₂—NCO, those represented byOCN—CH(CF₃)—R—CH(CF₃)—NCO, mixtures of these, and the like. In theformulas, R_(f) represents a perfluoroalkylene group containing 1 to 20carbon atoms, which may optionally contain one or more ether bonds, andR represents an alkylene group containing 1 to 18 carbon atoms, whichmay optionally contain one or more ether bonds.

As those represented by OCN—R_(f)—NCO, there may be mentioneddifluoromethylene diisocyanate, perfluorodimethylene diisocyanate,perfluorotrimethylene diisocyanate, perfluoroeicosa diisocyanate,bis(isocyanatoperfluoroethyl) ether, bis(diisocyanatoperfluoroisoproyl)ether, and the like.

As those represented by OCN—CH₂—R_(f)—CH₂—NCO, there may be mentionedbis(isocyanatomethyl)difluoromethane,bis(isocyanatomethyl)perfluoroethane,bis(isocyanatomethyl)perfluoropropane,bis(isocyanatomethyl)perfluorobutane (FHMDI),bis(isocyanatomethyl)perfluoropentane,bis(isocyanatomethyl)perfluorohexane,bis(isocyanatomethyl)perfluoroeicosane,bis(isocyanatomethylperfluoroethyl) ether, and the like.

As those represented by OCN—CF₂—R—CF₂—NCO, there may be mentionedbis(isocyanatodifluoromethyl)methane,bis(isocyanatodifluoromethyl)propane,bis(isocyanatodifluoromethyl)octadecane,2,2′-bis(isocyanatodifluoromethylethyl) ether, and the like.

As those represented by OCN—CH₂—CF₂—R—CF₂—CH₂—NCO, there may bementioned bis(2-isocyanato-1,1-difluoroethyl)methane,bis(2-isocyanato-1,1-difluoroethyl)propane,bis(2-isocyanato-1,1-difluoroethyl)hexadecane,bis(2-isocyanato-1,1-difluoroethylethyl) ether, and the like.

As those represented by OCN—CH(CF₃)—R—CH(CF₃)—NCO, there may bementioned diisocyanato-1,1,1,4,4,4-hexafluoropentane,bis(isocyanato-3,3,3-trifluoropropyl) ether, and the like.

Employable as the alicyclic polyisocyanates are fluorine-free alicyclicpolyisocyanates, fluorine-containing alicyclic polyisocyanates and thelike.

As the fluorine-free alicyclic polyisocyanates, there may be mentionedisophoronediisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate(hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylenediisocyanate (hydrogenated TDI),4,4′,4″-tricyclohexylmethanetriisocyanate, bis(2-isocyanatoethyl)4-cyclehexene-1,2-dicarboxylate, 2,5- or 2,6-norbornanediisocyanate,mixture of these, and the like.

As the fluorine-containing alicyclic polyisocyanates, there may bementioned diisocyanatoperfluorocyclohexane,diisocyanatotetrafluorocyclohexane,bis(isocyanatomethyl)perfluorocyclohexane,bis(isocyanatomethyl)tetrafluorocyclohexane,bis(isocyanatomethyl)perfluorodimethylcyclohexane,bis(isocyanatomethyl)dimethyltetrafluorocyclohexane,bis(isocyanatodifluoromethyl)cyclohexane,bis(isocyanatoperfluorocyclohexyl),bis(isocyanatotetrafluorocyclohexyl),bis(isocyanatoperfluorocyclohexyl)perfluoropropane,bis(isocyanatotetrafluorocyclohexyl)perfluoropropane,bis(isocyanatomethylperfluorocyclohexyl)perfluoropropane,bis(isocyanatomethyltetrafluorocyclohexyl)perfluoropropane,bis(2-isocyanato-1,1-difluoroethyl)cyclohexane,bis(2-isocyanato-1,1-difluoroethyl)cyclohexane, mixtures of these, andthe like.

Employable as the araliphatic polyisocyanates are fluorine-freearaliphatic polyisocyanates, fluorine-containing araliphaticpolyisocyanates, and the like.

As the fluorine-free araliphatic polyisocyanates, there may be mentionedm- or p-xylylene diisocyanate (XDI), α, α, α′, α′-tetramethylxylylenediisocyanate (TMXDI), α, α, α′, α′-tetraethylxylylene diisocyanate(TMXDI), mixtures of these, and the like.

As the fluorine-containing araliphatic polyisocyanates, there may bementioned bis(isocyanatomethyl)perfluorobenzene,bis(isocyanatomethyl)dimethylperfluorobenzene,bis(isocyanatoperfluorophenyl)perfluoropropane,bis(isocyanatomethylperfluorophenyl)perfluoropropane,bis(2-isocyanato-2,2-difluoroethyl)benzene,bis(2-isocyanato-1,1-difluoroethyl)benzene, mixtures of these, and thelike.

As the modifications of these, there may be mentioned modifications ofHDI (urethane-modified HDI, carbodiimide-modified HDI, trihydrocarbylphosphate-modified HDI, etc.), modifications of FHMDI (urethane-modifiedFHMDI, carbodiimide-modified FHMDI, trihydrocarbyl phosphate-modifiedFHMDI, etc.), modifications of MDI (urethane-modified MDI,carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.),modifications of TDI (urethane-modified TDI, carbodiimide-modified TDI,trihydrocarbyl phosphate-modified TDI, etc.), mixtures of these, and thelike.

Also preferably employable as the polyisocyanate (A) in addition tothose enumerated above are tertiary amino group-containingpolyisocyanates [N,N-bis(isocyanatoethyl)methylamine,N,N-bis(4-isocyanatocyclohexyl)methylamine, etc.], quaternary ammoniogroup-containing polyisocyanates[N,N-bis(isocyanatoethyl)dimethylammonium chloride,N,N-bis(4-isocyanatocyclohexyl)dimethylammonium chloride, etc.], and thelike. The use of these polyisocyanates results in a further increase incurability.

Preferred as the polyisocyanate (A), from the viewpoint of safety of (A)and the like, are aliphatic polyisocyanates, alicyclic polyisocyanates,tertiary amino group-containing polyisocyanates and quaternary ammoniogroup-containing polyisocyanates. More preferred from the reactivity andthe like viewpoint are fluorine-containing aliphatic polyisocyanates,fluorine-containing alicyclic polyisocyanates, tertiary aminogroup-containing polyisocyanates and quaternary ammonio group-containingpolyisocyanates. Especially preferred are fluorine-containing aliphaticpolyisocyanates and fluorine-containing alicyclic polyisocyanates. Mostpreferred are those represented by OCN—CH₂—R_(f)—CH₂—NCO.

The active hydrogen-containing polymer (B) includes polyethers {hydroxylgroup-containing polyethers (B1), mercapto group-containing polyethers(B2), primary and/or secondary amino group-containing polyethers (B3)and carboxyl group-containing polyethers (B4)}, polyesters {hydroxylgroup-containing polyesters (B5), mercapto group-containingpoly(thio)esters (B6), primary and/or secondary amino group-containingpolyesters (B7) and carboxyl group-containing polyesters (B8)},polyamides {hydroxyl group-containing polyamides (B9), mercaptogroup-containing polyamides (B10), primary and/or secondary aminogroup-containing polyamides (B11) and carboxyl group-containingpolyamides (B12)}, and the like.

Employable as the hydroxyl group-containing polyethers (B1) are alkyleneoxide (co)adducts derived from compounds (b) having at least two activehydrogen atoms.

As the alkylene oxide, there may be mentioned alkylene oxides containing2 to 8 carbon atoms (ethylene oxide, propylene oxide, butylene oxide,tetrahydrofuran, styrene oxide, etc.), fluoroalkylene oxides containing2 to 8 carbon atoms (1,1-difluoroethylene oxide, tetrafluoroethyleneoxide, 3,3,3-trifluoropropylene oxide, perfluoropropylene oxide,perfluorobutylene oxide, perfluorotetrahydrofuran, perfluorostyreneoxide, etc.), and the like. Preferred as the alkylene oxide are ethyleneoxide and propylene oxide, and the use of ethylene oxide alone or of amixture of ethylene oxide and propylene oxide is preferred.

In the case of coadducts, the mode of addition may be a random or blockmode, or a combination thereof. Preferred is a random one.

In cases where a fluoroethylene oxide and/or a fluoroalkylene oxide isused, it is preferred that such fluoroethylene oxide and/orfluoroalkylene oxide be subjected to addition reaction after reaction ofethylene oxide and/or an alkylene oxide with (b). The existence of afluorine compound at termini contributes to a further increase incurability of the isocyanato group-containing polymer. Among thefluoroethylene oxides and fluoroalkylene oxides, 1,1-difluoroethyleneoxide, perfluoroethylne oxide and 3,3,3-trifluoropropylene oxide arepreferred, and 3,3,3-trifluoropropylene oxide is more preferred.

In the case of coadducts, the ethylene oxide content (in % by weight)based on the coadduct weight is preferably not lower than 30, morepreferably not lower than 50, particularly preferably not lower than 60,most preferably not lower than 70, while it is preferably not higherthan 100, more preferably not higher than 98, particularly preferablynot higher than 95, most preferably not higher than 90. Within the aboverange, adhesive strength (in particular in initial adhesive strength)becomes higher.

Employable as the compound (b) having at least two active hydrogen atomsare water, diols, tri- to hexa- or further hydric polyols, dicarboxylicacids, tri- to tetra- or further basic polycarboxylic acids, monoamines,polyamines, polythiols and the like. When a compound having two activehydrogen atoms is used, dihydric polyols are obtained and, when acompound having three or more active hydrogen atoms is used, tri- orfurther hydric polyols are obtained.

Employable as the diols are alkylene glycols containing 2 to 30 carbonatoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol,1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol,tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.);alicyclic diols containing 6 to 24 carbon atoms(1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenolscontaining 15 to 30 carbon atoms (bisphenol A, bisphenol F, bisphenol S,etc.); dihydroxybenzenes (catechol, hydroquinone, etc.); polyester diolshaving a weight average molecular weight (Mw) of 100 to 5,000[polylactone diols (poly-ε-caprolactone diol, etc.), aliphatic polyesterdiols (ethylene glycol/adipic acid polyester diol, butyleneglycol/adipic acid polyester diol, etc.), aromatic polyester diols(ethylene glycol/terephthalic acid polyester diol etc.), etc.), andpolybutadiene diols having an Mw of 1,000 to 20,000; and the like. TheMw can be determined by gel permeation chromatography (GPC) usingpolyethylene glycol species or polystyrene species as standardsubstances.

Employable as the tri- to hexahydric polyols are aliphatic polyhydric(tri- to hexahydric) alcohols containing 3 to 8 carbon atoms (glycerol,trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan,sorbitol, etc.), and the like.

Employable as the dicarboxylic acids are alkanedicarboxylic acidscontaining 4 to 32 carbon atoms (succinic acid, adipic acid, sebacicacid, dodecenylsuccinic acid, azelaic acid, sebacic acid,dodecanedicarboxylic acid, octadecanedicarboxylic acid, dodecylsuccinicacid, octadecylsuccinic acid, etc.); alkenedicarboxylic acids containing4 to 32 carbon atoms (maleic acid, fumaric acid, citraconic acid,mesaconic acid, dimer acid, dodecenylsuccinic acid, pentadecenylsuccinicacid, etc.); aromatic dicarboxylic acids containing 8 to 20 carbon atoms(phthalic acid, isophthalic acid, terephthalic acid,naphthalenedicarboxylic acid, etc.); and the like.

Employable as the tri- or tetrabasic or further basic polycarboxylicacids are aromatic polycarboxylic acids (trimellitic acid, pyromelliticacid, etc.), and the like.

These dicarboxylic acids or polycarboxylic acids may be used in the formof acid anhydrides, lower alkyl esters or the like as well. As the acidanhydrides of these dicarboxylic acids or polycarboxylic acids, theremay be mentioned maleic anhydride, phthalic anhydride, trimelliticanhydride, pyromellitic anhydride, and the like. Usable as the loweralkyl are alkyl groups containing 1 to 4 carbon atoms. Thus, methyl,ethyl, isopropyl, tert-butyl and the like may be mentioned.

Employable as the monoamines are ammonia; aliphatic amines containing 1to 20 carbon atoms {alkylamines containing 1 to 20 carbon atoms(methylamine, ethylamine, propylamine, hexylamine, dedecylamine,eicosylamine, etc.) etc.}; alicylic amines containing 4 to 15 carbonatoms (aminocyclohexane, isophoronemonoamine and4-methylenedicyclohexanemonoamine); heterocyclic amines containing 4 to15 carbon atoms (piperidine, N-aminoethylpyridine, etc.); aromaticring-containing aliphatic amines containing 6 to 15 carbon atoms(aminomethylbenzene etc.); aromatic amines containing 6 to 15 carbonatoms (aniline etc.); and the like.

Employable as the polyamines are aliphatic polyamines containing 2 to 18carbon atoms {alkylenediamines containing 2 to 12 carbon atoms(ethylenediamine, propylenediamine, trimethylenediamine,hexamethylenediamine, undecylenediamine, etc.), polyalkylenepolyamines(alkylene has 2 to 6 carbon atoms) (diethylenetriamine,dipropylenetriamine, triethylenetetramine, pentaethylenehexamine, etc.),and the like}, alicyclic polyamines containing 4 to 15 carbon atoms(1,3-diaminocyclohexane, isophoronediamine and4,4′-methylenedicyclohexanediamine); heterocyclic polyamines containing4 to 15 carbon atoms (piperazine, N-aminoethylpiperazine,1,4-diaminoethylpiperazine, etc.); aromatic ring-containing aliphaticamines containing 8 to 15 carbon atoms (xylylenediamine,tetrachloro-p-xylylenediamine, etc.); aromatic polyamines containing 6to 20 carbon atoms (phenylenediamine, bis(aminophenyl)methane,4-aminophenyl-2-chloroaniline, 1-methyl-2-methylamino-4-aminobenzene,etc.); and the like.

Employable as the polythiols are hydrogen sulfide, polythiols containing1 to 24 carbon atoms (methanedithiol, ethanedithiol, 1,4-butanedithiol,1,6-hexanedithiol, 1,2,3-propanetrithiol, etc.) and the like.

In addition to those compounds, aminocarboxylic acids, hydroxycarboxylicacids, amino alcohols and the like can also be used as the compound (b)having at least two active hydrogen atoms.

Among those compounds (b) having at least two active hydrogen atoms,diols are preferred, alkylene glycols are more preferred, alkyleneglycols containing 2 to 30 carbon atoms are particularly preferred, andalkylene glycols containing 2 to 4 carbon atoms (ethylene glycol,1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, etc.) aremost preferred.

An amino group-containing compound (b1) having at least two activehydrogen atoms, a quaternary ammonio group-containing compound (b2)having at least two active hydrogen atoms, mixtures of these, and thelike can also be preferably used as the compound (b) having at least twoactive hydrogen atoms. When (b1) or (b2) is used, the reactivity of thepolymer becomes higher.

Usable as the compound (b1) are monoamines, polyamines, and the like. Asthe monoamines, there may be mentioned ammonia and monoamino compoundscontaining 1 to 20 carbon atoms [aliphatic amines (methylamine,ethylamine, propylamine, hexylamine, dodecylamine, eicosylamine, etc.);alicyclic amines (cyclohexylamine, isophoronemonoamine,4-cyclohexylmethylcyclohexylamine, 4-dicyclohexylmethylcyclohexylamine,etc.); heterocyclic amines (piperidine, N-aminoethylpiperidine, etc.);aromatic ring-containing aliphatic amines (aminomethylbenzene etc.);aromatic amines (aniline etc.), etc.]; and the like.

As the polyamines, there may be mentioned polyamines containing 2 to 18carbon atoms {aliphatic polyamines [alkylenediamines (ethylenediamine,propylenediamine, trimethylenediamine, hexamethylenediamine,undecylenediamine, etc.), dialkylaminoalkylamines(dimethylaminoethylamine, diethylaminopropylamine,dipropylaminopropylamine, methylethylaminopropylamine anddioctadecylaminoethylamine), N,N′-dialkylalkylenediamines(N,N′-dimethylethylenediamine etc.), polyalkylenepolyamines(diethylenetriamine, dipropylenetriamine, triethylenetetramine,pentaethylenehexamine, etc.), etc.]; alicyclic polyamines(1,3-diaminocyclohexane, isophoronediamine and4,4′-methylenedicyclohexanediamine); heterocyclic polyamines(piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, etc.);aromatic ring-containing aliphatic amines (xylylenediamine,tetrachloro-p-xylylenediamine, etc.); aromatic polyamines(phenylenediamine, bis(aminophenyl)methane,4-aminophenyl-2-chloroaniline, 1-methyl-2-methylamino-4-aminobenzene,etc.), etc.}; and the like.

Also preferably employable as the compound (b1) are tertiary aminogroup-containing polyols (2-dimethylaminopropanediol,2-diethylaminoethylpropanediol, dimethylaminoethylcyclohexanediol,etc.), tertiary amino group-containing polythiols[bis(mercaptoethyl)methylamine etc.], tertiary amino group-containingpolycarboxylic acids (2-dimethylaminoethyladipic acid etc.), and thelike. When these are used, the reactivity of the polymer becomes higher.

Preferred as the compound (b1) are aliphatic amines, alicyclic amines,dialkylaminoalkylamines and N,N′-dialkylalkylenediamines. More preferredare aliphatic amines, dialkylaminoalkylamines andN,N′-dialkylalkylenediamines. Most preferred aredialkylaminoalkylamines.

As the quaternary ammonio group-containing compound (b2) having at leasttwo active hydrogen atoms, there may be mentioned compounds resultingfrom conversion of the amino group or groups of the aminogroup-containing compound (b1) having at least two active hydrogen atomsto ammonium {Lewis acid salts of primary amines or secondary amines,Broensted acid salts of tertiary amines [monoamine salts(dimethylammonium chloride, N-methyl-N-cyclohexylammonium methylsulfate, etc.), polyamine salts (tetramethylethylenediammoniumbisnitrate etc.)], quaternization products derived from tertiary aminogroup-containing polyols (2-trimethylammoniopropanediol chloride etc.),quaternization products derived from tertiary amino group-containingpolythiols [bis(mercaptoethyl)dimethylammonium chloride etc.]quaternization products derived from tertiary amino group-containingpolycarboxylic acids (2-trimethylammonioethyladipic acid chloride-etc.)etc.] etc.}, and the like.

As the Broensted acid, there may be mentioned hydrochloric acid, nitricacid, sulfuric acid, formic acid, acetic acid, benzoic acid and thelike, and as the Lewis acid, there may be mentioned such Broensted acidsand alkyl halides (alkyl has 1 to 20 carbon atoms) (methyl chloride,methyl bromide, ethyl chloride, decyl chloride, decyl bromide, eicosylchloride, benzyl chloride, benzyl bromide, epichlorohydrin, etc.),alkylated inorganic acids (alkyl has 1 to 7 carbon atoms) (dimethylsulfate, benzyl sulfate etc.), dialkyl carbonates (alkyl has 1 to 7carbon atoms) (dimethyl carbonate, dibenzyl carbonate, etc.), and thelike.

The hydroxyl group-containing polyethers (B1) preferably have a Mn ofnot lower than 200, more preferably not lower than 300, most preferablynot lower than 400, and preferably not higher than 10,000, morepreferably not higher than 8,000, most preferably not higher than 6,000.Within such range, the adhesive strength (in particular wet adhesivestrength) becomes higher.

Employable as the mercapto group-containing polyethers (B2) are thoseones having a structure resulting from conversion of at least onehydroxyl group of the hydroxyl group-containing polyether (B1) to amercapto group, and the like, including those ones having a structureobtained by reacting the hydroxyl group-containing polyether (B1) withan epihalohydrin (e.g. epichlorohydrin etc.), followed by reaction withhydrogen sulfide, those ones having a structure obtained by directlyreacting the hydroxyl group-containing polyether (B1) with a cyclicthioether (e.g. ethylene sulfoxide etc.), and the like.

The mercapto group-containing polyethers (B2) preferably have a Mn ofnot lower than 200, more preferably not lower than 300, most preferablynot lower than 400, and preferably not higher than 10,000, morepreferably not higher than 8,000, most preferably not higher than 6,000.Within such range, the adhesive strength (in particular wet adhesivestrength) becomes higher.

Employable as the primary and/or secondary amino group-containingpolyethers (B3) are those ones having a structure resulting fromconversion of at least one hydroxyl group of the hydroxylgroup-containing polyether (B1) or at least one mercapto group of amercapto group-containing polyether (B2) to a primary and/or secondaryamino group, and the like, including those ones having a structureobtained by reacting (B1) or (B2) with a cyclic amine (e.g.ethylenimine, N-methylethylenimine and the like) and the like, thoseones having a structure resulting from (co)addition polymerization of analkylene oxide on a ketimine compound obtained from a hydroxylgroup-containing primary amine (e.g. ethanolamine etc.) and a ketone(e.g. methyl ethyl ketone etc.), followed by hydrolysis for ketoneelimination and conversion to a primary amine, and the like.

The primary and/or secondary amino group-containing polyethers (B3)preferably have a Mn of not lower than 200, more preferably not lowerthan 300, most preferably not lower than 400, and preferably not higherthan 10,000, more preferably not higher than 8,000, most preferably nothigher than 6,000. Within such range, the adhesive strength (inparticular wet adhesive strength) becomes higher.

Employable as the carboxyl group-containing polyethers (B4) are thoseones having a structure resulting from conversion of at least onehydroxyl group of the hydroxyl group-containing polyether (Bi) or atleast one mercapto group of the mercapto group-containing polyether (B2)to a carboxyl group, and the like, including those ones having astructure obtained by reacting (B1) or (B2) with the acid anhydride oran alkyl ester of such a dicarboxylic acid or polycarboxylic acid asmentioned above etc., those ones having a structure resulting fromconversion of a hydroxyl group(s) of (B1) to a carboxyl group(s) byoxidation in the presence of an oxidizing agent (e.g. platinum compound,chromic mixed acid, permanganate salts and the like), those ones havinga structure obtained by (co)addition polymerization of an alkylene oxidecontaining ethylene oxide as an essential constituent on a hydroxy acidlower alcohol ester (e.g. methyl lactate etc.), followed by hydrolysisfor alcohol elimination and conversion to a carboxyl group(s), and thelike.

The carboxyl group-containing polyethers (B4) preferably have a Mn ofnot lower than 200, more preferably not lower than 300, most preferablynot lower than 400, and preferably not higher than 10,000, morepreferably not higher than 8,000, most preferably not higher than 6,000.Within such range, the adhesive strength (in particular wet adhesivestrength) becomes higher.

Employable as the hydroxyl group-containing polyesters (B5) arepolyesters of (B1) with the above-mentioned dicarboxylic acids,dicarboxylic acid anhydrides and/or dicarboxylic acid lower alkylesters, and the like. The termini of these polyesters are hydroxylgroups. Polycarboxylic acids, polycarboxylic acid anhydrides,polycarboxylic acid lower alkyl esters and the like may also be usedand, when these are used, the proportion thereof (in mole percent) ispreferably 0.1 to 10, more preferably 0.1 to 5, most preferably 0.1 to2, based on the number of moles of all carboxylic acids. The (B1) to beused for obtaining (B5) is preferably one having a Mn of not lower than100 but not higher than 5,000.

The hydroxyl group-containing polyesters (B5) preferably have a Mn ofnot lower than 200, more preferably not lower than 300, most preferablynot lower than 400, and preferably not higher than 10,000, morepreferably not higher than 8,000, most preferably not higher than 6,000.Within such range, the adhesive strength (in particular wet adhesivestrength) becomes higher.

Employable as the mercapto group-containing poly(thio)ethers (B6) arethose ones having a structure resulting from conversion of at least onehydroxyl group of the hydroxyl group-containing polyester (B5) to amercapto group (those ones having a structure obtained by reacting thehydroxyl group-containing polyester (B5) with an epihalohydrin, followedby reaction with hydrogen sulfide, those ones having a structureobtained by directly reacting the hydroxyl group-containing polyester(B5) with a cyclic thio ether, etc.], polythioesters (with at least oneterminus being a mercapto group) producible from the mercaptogroup-containing polyethers (B2) and the above-mentioned dicarboxylicacids, dicarboxylic acid anhydrides and/or dicarboxylic acid lower alkylesters, and the like. The (B2) to be used for obtaining (B6) preferablyhas a Mn of not lower than 100 but not higher than 5,000.

The mercapto group-containing poly(thio)esters (B6) preferably have a Mnof not lower than 200, more preferably not lower than 300, mostpreferably not lower than 400, and preferably not higher than 10,000,more preferably not higher than 8,000, most preferably not higher than6,000. Within such range, the adhesive strength (in particular wetadhesive strength) becomes higher.

Employable as the primary and/or secondary amino group-containingpolyesters (B7) are those ones having a structure resulting fromconversion of at least one hydroxyl group of the hydroxylgroup-containing polyester (B5) to a primary and/or secondary aminogroup, and the like, including those ones having a structure obtained byreacting the hydroxyl group-containing polyester (B5) with a cyclicamine, and the like.

The primary and/or secondary amino group-containing polyethers (B7)preferably have a Mn of not lower than 200, more preferably not lowerthan 300, most preferably not lower than 400, and preferably not higherthan 10,000, more preferably not higher than 8,000, most preferably nothigher than 6,000. Within such range, the adhesive strength (inparticular wet adhesive strength) becomes higher.

Employable as the carboxyl group-containing polyesters (B8) are thoseones having a structure resulting from conversion of at least onehydroxyl group of the hydroxyl group-containing polyester (B5) to acarboxyl group [those ones having a structure obtained by reacting thehydroxy group-containing polyester (B5) with such a dicarboxylic acid,dicarboxylic acid anhydride and/or the like as mentioned above, thoseones having a structure (with at least one terminus being a carboxylgroup) obtained by reacting the carboxyl group-containing polyether (B4)with such a polyol as mentioned above, and the like, etc.], and thelike. The (B4) to be used for obtaining (B8) preferably has a Mn of notlower than 100 but not higher than 5,000.

The carboxyl group-containing polyesters (B8) preferably have a Mn ofnot lower than 200, more preferably not lower than 300, most preferablynot lower than 400, and preferably not higher than 10,000, morepreferably not higher than 8,000, most preferably not higher than 6,000.Within such range, the adhesive strength (in particular wet adhesivestrength) becomes higher.

Employable as the hydroxyl group-containing polyamides (B9) are thoseones having a structure resulting from conversion of at least one aminogroup or carboxyl group of a polyamide derived from the primary and/orsecondary amino group-containing polyether (B3) and such a dicarboxylicacid, di- or polycarboxylic acid anhydride and/or dicarboxylic acidlower alkyl ester as mentioned above, a polyamide derived from thecarboxyl group-containing polyether (B4) and such a polyamine asmentioned above, or the like to a hydroxyl group [those ones having astructure obtained by reacting such a polyamide with an alkylene oxide,those ones having a structure obtained by reacting such a polyamide withan epihalohydrin, followed by hydrolysis, etc.], and the like. The (B3)and (B4) to be used for obtaining (B9) each preferably has a Mn of notlower than 100 but not higher than 5,000.

The hydroxyl group-containing polyamides (B9) preferably have a Mn ofnot lower than 200, more preferably not lower than 300, most preferablynot lower than 400, and preferably not higher than 10,000, morepreferably not higher than 8,000, most preferably not higher than 6,000.

Within such range, the adhesive strength (in particular wet adhesivestrength) becomes higher.

Employable as the mercapto group-containing polyamides (B10) are thoseones having a structure resulting from conversion of at least one aminogroup or carboxyl group of a polyamide derived from the primary and/orsecondary amino group-containing polyether (B3) and such a dicarboxylicacid, di- or polycarboxylic acid anhydride and/or dicarboxylic acidlower alkyl ester as mentioned above, the polyamide derived from acarboxyl group-containing polyether (B4) and such a polyamine asmentioned above, or the like to a mercapto group [those ones having astructure obtained by reacting such a polyamide with an epihalohydrin,followed by reaction with hydrogen sulfide, those ones having astructure obtained by directly reacting such a polyamide with a cyclicthioether, etc.], and the like. The (B3) and (B4) to be used forobtaining (BlO) each preferably has a Mn of not lower than 100 but nothigher than 5,000.

The mercapto group-containing polyamides (B10) preferably have a Mn ofnot lower than 200, more preferably not lower than 300, most preferablynot lower than 400, and preferably not higher than 10,000, morepreferably not higher than 8,000, most preferably not higher than 6,000.Within such range, the adhesive strength (in particular wet adhesivestrength) becomes higher.

Employable as the primary and/or secondary amino group-containingpolyamides (B11) are those ones having a structure obtained by reactingthe primary and/or secondary amino group-containing polyether (B3) withsuch a dicarboxylic acid, di- or polycarboxylic acid anhydride and/ordicarboxylic acid lower alkyl ester as mentioned above (with at leastone terminus being a primary and/or secondary amino group), those oneshaving a structure obtained by reacting the carboxyl group-containingpolyether (B4) with such a polyamine as mentioned above (with at leastone terminus being a primary and/or secondary amino group), and thelike. The (B3) and (B4) to be used for obtaining (B11) each preferablyhas a Mn of not lower than 100 but not higher than 5,000.

The primary and/or secondary amino group-containing polyamides (B11)preferably have a Mn of not lower than 200, more preferably not lowerthan 300, most preferably not lower than 400, and preferably not higherthan 10,000, more preferably not higher than 8,000, most preferably nothigher than 6,000. Within such range, the adhesive strength (inparticular wet adhesive strength) becomes higher.

Employable as the carboxyl group-containing polyamides (B12) are thoseones having a structure obtained by reacting the primary and/orsecondary amino group-containing polyether (B3) with such a dicarboxylicacid, di- or polycarboxylic acid anhydride or dicarboxylic acid loweralkyl ester as mentioned above (with at least one terminus being acarboxyl group), those ones having a structure obtained by reacting thecarboxyl group-containing polyether (B4) with such a polyamine asmentioned above (with at least one terminus being a carboxyl group), andthe like. The (B3) and (B4) to be used for obtaining (B12) eachpreferably has a Mn of not lower than 100 but not higher than 5,000.

The carboxyl group-containing polyamides (B12) preferably have a Mn ofnot lower than 200, more preferably not lower than 300, most preferablynot lower than 400, and preferably not higher than 10,000, morepreferably not higher than 8,000, most preferably not higher than 6,000.Within such range, the adhesive strength (in particular wet adhesivestrength) becomes higher.

Preferred as the active hydrogen-containing polymer (B) are thosehydroxyl group- or mercapto group-containing ones {the hydroxylgroup-containing polyethers (B1), the mercapto group-containingpolyethers (B2), the hydroxy group-containing polyesters (B5), themercapto group-containing poly(thio)esters (B6), the hydroxylgroup-containing polyamides (B9) and the mercapto group-containingpolyamides (B10)}. More preferred are (B1), (B2), (B5) and (B6). Mostpreferred are (B1) and (B5).

Among the active hydrogen-containing polymers (B), those esterbond-containing ones (the carboxyl group-containing polyethers (B4), thehydroxyl group-containing polyesters (B5), the mercapto group-containingpoly(thio)esters (B6), the primary and/or secondary aminogroup-containing polyesters (B7), the carboxyl group-containingpolyesters (B8), etc.} have ready hydrolyzability, hence are preferablyused in those cases where the long-term in vivo existence of the polymerof the invention, when used in adhesion of vital tissues, is undesirablefor some or other reasons. When those ones having a bond represented by—R¹—(CH₂),—COO—are used as the active hydrogen-containing polymer (B),enhanced ready hydrolyzability preferably results. In the formula, nrepresents an integer of 0 to 2, and R¹ represents a carbonyl group oran electron-attracting characteristic group —C(X) (Y)—{X representing F,Cl, Br, NO₂ or CN and Y representing H, F, Cl, Br or CN}. When theactive hydrogen-containing polymer (B) having such a bond is used, theresulting polymer of the invention, when used in adhesion of vitaltissues, can show good hydrolyzability. As such activehydrogen-containing polymer (B), there may be mentioned esters ofa-ketoglutaric acid with polyethylene glycol (cf. Japanese KokaiPublication Hei-02-20 327392, Japanese Kokai Publication Hei-03-163590or the like), and the like.

From the adhesive strength (in particular initial adhesive strength) andthe like viewpoint, the active hydrogen-containing polymer (B) ispreferably a hydrophilic polymer. The term “hydrophilic polymer” means apolymer having a polyoxyethylene group content of not lower than 30% byweight per molecule or one comparable in affinity for water thereto. Incases where an active hydrogen-containing polymer which is not ahydrophilic one is used, the content (in % by weight) of this activehydrogen-containing polymer is preferably not lower than 1, morepreferably not lower than 2, particularly preferably not lower than 5,most preferably not lower than 8, and preferably not higher than 70,more preferably not higher than 50, particularly preferably not higherthan 20, most preferably not higher than 15, based on the total weightof the active hydrogen-containing polymer (B), from the adhesivestrength (in particular initial adhesive strength) and the likeviewpoint. The oxyethylene group content (in % by weight) in the activehydrogen-containing polymer (B) is preferably not lower than 30, morepreferably not lower than 50, particularly preferably not lower than 65,most preferably not lower than 70, and preferably not higher than 100,more preferably not higher than 98, particularly preferably not higherthan 95, most preferably not higher than 90, based on the weight of (B).When the content of the active hydrogen-containing polymer which is nothydrophilic and the oxyethylene group content are within such respectiveranges, the adhesive strength (in particular initial adhesive strength)becomes higher.

From the adhesive strength (in particular wet adhesive strength) and thelike viewpoint, the active hydrogen-containing polymer (B) preferablyhas an active hydrogen equivalent (molecular weight per equivalent ofactive hydrogen) of not less than 50, more preferably not less than 100,most preferably not less than 200, and preferably not more than 5,000,more preferably not more than 4,000, most preferably not more than3,000. The active hydrogen equivalent can be determined by treatmentwith an excess amount of a carboxylic acid anhydride (e.g. aceticanhydride etc.), titrating the unreacted carboxylic acid anhydride withan aqueous solution of potassium hydroxide and the like, and calculatingthe number of moles of the functional group per unit weight.

The active hydrogen-containing polymer (B) preferably has a Mn of notlower than 200, more preferably not lower than 300, particularlypreferably not lower than 400, most preferably not lower than 1,000, andpreferably not higher than 10,000, more preferably not higher than8,000, particularly preferably not higher than 6,000, most preferablynot higher than 4,000. Within such range, the adhesive strength (inparticular wet adhesive strength) becomes higher.

Preferred as the active hydrogen-containing polymer (B), from theadhesive strength (in particular initial adhesive strength) and the likeviewpoint, are ethylene oxide-propylene oxide random copolymers, andmixtures of ethylene oxide-propylene oxide random copolymers andpropylene oxide polymers. Most preferred are mixtures of ethyleneoxide-propylene oxide random copolymers and propylene oxide polymers.Most preferred as the ethylene oxide-propylene oxide random copolymersare those ones produced using water, ethylene glycol and/or propyleneglycol as an active hydrogen-containing compound and having a Mn of1,000 to 6,000 and an oxyethylene group content of 60 to 90% by weight.

When a trivalent or further polyvalent active hydrogen-containingpolymer is used as the active hydrogen-containing polymer (B), thecontent thereof (in % by weight) is preferably not lower than 0.01, morepreferably not lower than 0.1, most preferably not lower than 0.2, andpreferably not higher than 5, more preferably not higher than 1, mostpreferably not higher than 0.8, based on the weight of thepolyisocyanate (A). Within such range, the adhesive strength (inparticular wet adhesive strength) becomes higher.

The alkali metal and alkaline earth metal content (in mmol/kg) in theactive hydrogen-containing polymer (B) is preferably 0 (zero) or below0.07, more preferably 0 or below 0.04, particularly preferably 0 orbelow 0.02, most preferably 0 or below 0.01, based on the weight of (B).Within such range, it is easy to prevent some or other abnormalreactions from occurring in the reaction between the isocyanate (A) andthe active hydrogen-containing polymer (B). The alkali metal andalkaline earth metal content in the active hydrogen-containing polymer(B) can be determined by subjecting a 30% (by weight) methanol solutionof (B) or an aqueous solution prepared by heating and incinerating 10 gof (B) on, a platinum dish and dissolving the ash in 10 g of water toion chromatography, by titrating a solution prepared by dissolving 30 gof (B) in 100 ml of methanol with {fraction (1/100)} N aqueoushydrochloric acid, or by the like method.

The alkali metal or alkaline earth metal is admixed mainly as a catalystin polyether polyol synthesis. As such catalyst, there may be mentionedhydroxides (potassium hydroxide, sodium hydroxide, cesium hydroxide,beryllium hydroxide, magnesium hydroxide, etc.), alcoholates (lithiummethylate, sodium ethylate, potassium butylate, magnesium hexylate,etc.), simple substance metals (potassium, sodium, lithium, magnesium,calcium, etc.), and the like. In many instances, such a catalyst remainsin the active hydrogen-containing polymer (B) in an amount of 0.1 to 0.3mmol/kg. Therefore, it is recommended that a polyether polyol low inalkali metal and alkaline earth metal content, and the like, be used sothat the alkali metal and alkaline earth metal content in the activehydrogen-containing polymer (B) may fall within the above range.

Such polyether polyol low in alkali metal and alkaline earth metalcontent can be obtained by removing the alkali metal and alkaline earthmetal catalysts from a crude polyether polyol obtained by additionpolymerization of an alkylene oxide on an active hydrogen-containingcompound in the presence of such a catalyst as mentioned above,by-carrying out the alkylene oxide addition polymerization reaction inthe presence of an alkali metal- and alkaline earth metal-free catalyst,such as a composite metal cyanide complex (e.g. zinchexacyanocobaltate-polyether complex catalyst etc.), an organoboroncompound [e.g. trifluoroboric acid, tris(pentafluorophenyl)borane etc.]or a transition metal complex catalyst, as disclosed in Japanese KokaiPublication Hei-08-104741, or by the like method. As the method ofalkali metal and alkaline earth metal elimination from the crudepolyether polyol, there may be mentioned the method comprising treatmentwith an adsorbent, the method comprising treatment with an ionexchanger, and the like method.

As the adsorbent, there may be mentioned silicates (magnesium silicate,talc, soapstone, stealite, calcium silicate, magnesium aluminosilicate,sodium aluminosilicate, etc.), clay species (activated clay, acid clay,etc.), hydrotalcite, silica gel, diatomaceous earth, activated aluminaand the like. Among these adsorbents, silicate salts are preferred, andmagnesium silicate is more preferred.

Among the magnesium silicate species, synthetic magnesium silicatespecies are preferred. More preferred are magnesium silicate specieshaving a sodium content of not higher than 0.5% by weight, as disclosedin Japanese Kokai Publication Hei-07-258403.

The adsorption treatment can be carried out by adding water andmagnesium silicate to and mixing them with the crude polyether polyol,as described in Japanese Kokai Publication Hei-07-258403.

The level of addition of water is preferably 0.01 to 50% by weightrelative to the crude polyether polyol, and the level of addition ofmagnesium silicate is 0.01 to 50% by weight on the same basis. Theadsorption treatment temperature is not particularly restricted butpreferably 60 to 200° C., and the oxygen concentration in the gaseousphase is preferably not higher than 1,000 ppm. The adsorption treatmenttime is not particularly restricted but preferably is 0.5 to 24 hours.After adsorption treatment, the treatment mixture is filtered through afilter paper, filter cloth, glass filter or like filtration apparatus,optionally followed by dehydration, whereby an activehydrogen-containing polymer (B) low in alkali metal and alkaline earthmetal content can be produced. In case the alkali metal and alkalineearth metal content is above the above range even after adsorptiontreatment, the alkali metal and alkaline earth metal content can bereduced by carrying out the adsorption treatment again.

As the ion exchanger, there may be mentioned strong cation exchangeresins, weak cation exchange resins, chelating resins, and the like. Asthe method of ion exchange treatment, there may be mentioned the methodcomprising adding water to the crude polyether polyol, admixing an ionexchanger with the mixture with stirring and removing the ion exchangerby filtration, the method comprising passage through a column packedwith an ion exchanger, or the like method. The level of addition ofwater (in % by weight) is preferably not lower than 0.01, morepreferably not lower than 1, and preferably not higher than 80, morepreferably not higher than 60, based on the weight of the crudepolyether polyol. The usage of the ion exchanger is preferably not lowerthan 0.1% by weight, more preferably not lower than 1%, and preferablynot higher than 50% by weight, more preferably not higher than 30% byweight, based on the weight of the aqueous solution mentioned above. Themixing temperature (in ° C.) is preferably not lower than 5, morepreferably not lower than 20, and preferably not higher than 80, morepreferably not higher than 40. The mixing time (in hours) is preferablyXnot shorter than 1, more preferably not shorter than 5, most preferablyshorter than 24.

In carrying out the filtration, such a filtration apparatus as a filterpaper, filter cloth or glass filter is used.

On the occasion of passage through a column packed with an ionexchanger, the liquid temperature (in ° C.) is preferably not lower than5, more preferably not lower than 20, and preferably not higher than 80,more preferably not higher than 40. Although one passage through thecolumn will be sufficient, the passage through the column may berepeated two to fifty times. As the method of dehydration to be carriedout according to need, there may be mentioned the method comprisingdistilling off water at 50 to 150° C. and 0.001 hPa to ordinary pressurefor 1 to 10 hours, optionally while passing an inert gas such asnitrogen, and the like method.

In cases where the active hydrogen-containing polymer (B) is a tertiaryamino group- and/or quaternary ammonio group-containing one, the contentof such group (number of groups/g) is preferably not smaller than1×10¹⁷, more preferably not smaller than 1×10¹⁸, most preferably notsmaller than 1×10¹⁹, and preferably not greater than 1×10²³, morepreferably not greater than 1×10²², most preferably not greater than1×10²¹, based on the weight of (B) from the polymer curability and thelike viewpoint. The number of tertiary amino groups and quaternaryammonio groups can be determined by calculation based on ¹H-NMR data orby potentiometric titration with {fraction (1/100)} N aqueoushydrochloric acid following sample treatment with excess aqueous sodiumhydroxide.

As the tertiary amino group- and/or quaternary ammonio group-containing,and active hydrogen-containing polymer, there may be mentioned thoseones having a structure obtained by addition of an alkylene oxide to theamino group-containing compound (b1) having at least two active hydrogenatoms, the quaternary ammonio group-containing compound (b2) having atleast two active hydrogen atoms and a mixture of these, and the like.

The urethane prepolymer (UP) is obtained by reacting the polyisocyanate(A) with the active hydrogen-containing polymer (B). The usage ratiobetween the polyisocyanate (A) and the active hydrogen-containingpolymer (B) as expressed in terms of equivalent ratio (A/B) between theisocyanato groups in (A) and the active hydrogen atoms in (B) ispreferably not lower than 1.5, more preferably not lower than 1.8,particularly preferably not lower than 1.9, most preferably not lowerthan 1.95, and preferably not higher than 5.0, more preferably nothigher than 3.0, particularly preferably not higher than 2.3, furtherpreferably not higher than 2.1, most preferably not higher than 2.0.Within such range, the adhesive strength (in particular initial adhesivestrength) becomes higher.

The urethane prepolymer (UP) can be produced by a method known in theart, for example by applying the method comprising mixing thepolyisocyanate (A) and the active hydrogen-containing polymer (B)together and allowing the reaction to proceed at 50 to 100° C. for 1 to10 hours, and the like method. Since, upon reaction with water, theisocyanato groups in (A) are converted to amino groups, it is necessaryto eliminate water in the reaction vessel and raw materials as far aspossible in the production process. Therefore, it is desirable that (B)be reacted with (A) after dehydration of (B). Applicable as the methodof dehydration are the method comprising distilling off water at 50 to150° C. and 0.001 hPa to ordinary pressure for 1 to 10 hours, optionallywhile passing an inert gas such as nitrogen, and the like method.

The method of mixing the polyisocyanate (A) and the activehydrogen-containing polymer (B) may be (1) the one comprising mixingthem together all at once, (2) the one comprising gradual dropwiseaddition of (B), or (3) the one comprising mixing (A) with a part of (B)and, after a predetermined period of reaction, adding the remainingportion of (B) dropwise or all at once. Among these, the methods (1) and(2) are preferred because of ease of reaction procedure and, from thisviewpoint, the method (1) is more preferred. From the viewpoint that theamount of the unreacted polyisocyanate component can be reduced, themethod (3) is preferred.

This reaction may be carried out in the presence of a catalyst (e.g. anorganometallic compound such as dibutyltin oxide or dibutyltindilaurate, an organic acid metal salt such as zirconium acetate, or thelike), and this mode of reaction is effective particularly in caseswhere an aliphatic isocyanate is used.

The urethane prepolymer (UP) preferably has a Mn of not lower than 500,more preferably not lower than 800, particularly preferably not lowerthan 1,000, most preferably not lower than 1,200, and preferably nothigher than 500,000, more preferably not higher than 100,000,particularly preferably not higher than 10,000, most preferably nothigher than 5,000. Within such range, the adhesive strength (inparticular wet adhesive strength) becomes higher. The content (in % byweight) of the urethane prepolymer having a Mn of 500 to 500,000 ispreferably not lower than 98 but not higher than 100, more preferablynot lower than 98.5, particularly preferably not lower than 99, mostpreferably not lower than 99.5, based on the weight of (UP). Within suchrange, the adhesive strength of the adhesive becomes higher.

The content of those urethane prepolymer molecules whose molecularweight is within a specific range (isocyanato group-containing urethanepolymers) in the urethane prepolymer (UP) can be estimated by comparingthe molecular weight distribution curve for urethane prepolymermolecules having a Mn of 500 to 500,000 as obtained by GPC, using anultraviolet detector, of the product of reaction with an amine havingone primary or secondary amino group and capable of absorbing light atwavelengths in the ultraviolet region (e.g. 4-aminopyridine,aminonaphthalene etc.) (standard substances:N-methylaminopyridine-ethylene oxide adducts) and the molecular weightdistribution curve obtained by GPC using a refractive index detectorfollowing reaction with an amine having one primary or secondary aminogroup and incapable of absorbing light at wavelengths in the ultravioletregion (e.g. ethylamine, dibutylamine etc.) (standard substances:polyethylene glycols). Thus, taking the functional groups of the polymerinto consideration, the determination can be realized by following theprocedure comprising the following steps (1) to (5) in that order:

-   (1) The urethane prepolymer (UP) is mixed with an amine having one    primary or secondary amino group and incapable of absorbing light at    wavelengths in the ultraviolet region (e.g. ethylamine, dibutylamine    etc.) to allow the reaction between the amino group and the    isocyanato group to proceed, and the reaction product is subjected    to GPC using a refractive index detector for Mn determination.-   (2) The average number of isocyanato groups per molecule (AN) is    determined based on the isocyanato group content (% by weight).-   (3) (UP) is mixed with an amine having one primary or secondary    amino group and capable of absorbing light at wavelengths in the    ultraviolet region (e.g. 4-aminopyridine, aminonaphthalene etc.) for    reaction with the isocyanato group, and the product having the    functional group capable of absorbing light at wavelengths in the    ultraviolet region (UVF) as introduced therein is subjected to GPC    using an ultraviolet detector for Mn determination. The molecular    weight distribution is determined by comparing with the standard    substances.-   (4) Based on this molecular weight distribution, the number of    functional groups in urethane prepolymer molecules with a Mn of 500    to 500,000 (UVF) is calculated.-   (5) From this and the average number (AN), the content of those    urethane prepolymer molecules having a Mn of 500 to 500,000 as    contained in the urethane prepolymer (UP) is estimated. The standard    substances corresponding to typical molecular weights can be    obtained by fractionation of the product of the addition of ethylene    oxide to N-methylaminopyridine or the like by preparative GPC.

A method of obtaining a polymer in which the content of urethaneprepolymer molecules having a Mn of 500 to 500,000 is 98 to 100% byweight comprises mixing the polyisocyanate (A) mentioned above with apart of the active hydrogen-containing polymer (B) and, after apredetermined period of reaction, admixing the remaining portion of (B)dropwise or all at once. Alternatively, by removing unreacted (A) aftercompletion of the above reaction, it is also possible to increase thecontent of urethane prepolymer molecules having a Mn of 500 to 500,000to 98 to 100% by weight. As the method of removing unreacted (A), theremay be mentioned (1) the method consisting in fractionation using GPC,(2) the method consisting in dialysis using a semipermeable membrane,(3) the method consisting in distilling off, and the like method. Fromthe ease of operation viewpoint, the distillation method (3) ispreferred. As for the process for distilling off, there may be mentionedthe process comprising distilling off unreacted (A) in the manner ofreduced pressure distillation (1 to 10 hours of distillation at 50 to150° C. and 0.001 hPa to ordinary pressure, optionally while passing aninert gas such as nitrogen), and the like process.

As the non-polyisocyanate-based polymer (NUP) having a structureresulting from conversion of one or more of the functional groups in theactive hydrogen-containing polymer to an isocyanato group, among theisocyanato group-containing polymers, there may be mentioned those oneshaving a structure obtainable by converting one or more of thefunctional groups of the above-mentioned active hydrogen-containingpolymer (B) directly to isocyanato groups, by introducing the isocyanatogroup(s) via an ether bond and/or ester bond, and by the like method,and the like.

In converting at least one of the functional groups (hydroxyl, mercapto,carboxyl, amino and the like groups) of the active hydrogen-containingpolymer (B) to an isocyanato group, any of the methods known in the artand the like method can be applied. Thus, in the case of a primaryhydroxyl or primary mercapto group, there may be mentioned (1) themethod involving conversion to an isocyanato group via an acid azide andthus comprising converting the functional group to a carboxyl group byoxidation and further to an acid halide, followed by reaction with anazide compound and further by thermal decomposition (e.g. Japanese KokaiPublication Sho-57-108055 etc.), (2) the method comprising convertingthe functional group to a carboxyl group by oxidation, convertingthus-obtained carboxyl group to an amino group using an azide compound,and converting the resulting amino group to an isocyanato group, and thelike method. In the case of a secondary hydroxyl or secondary mercaptogroup, there may be mentioned (3) the method comprising converting thefunctional group to a carbonyl group by oxidation, converting this to anamino group by reaction with ammonia and simultaneous reduction withhydrogen, and converting this amino group to an isocyanato group, andthe like method. In the case of a primary or secondary hydroxyl orprimary or secondary mercapto group, there may be mentioned (4) themethod comprising converting the functional group to an amino group,followed by reaction with phosgene for conversion to an isocyanatogroup, (5) the method comprising reacting (B) with an isocyanatogroup-containing unsaturated compound, and the like method. Furthermore,when the functional group is a carboxyl group, those steps of the method(1) or (2) which follow the conversion to a carboxyl group can beapplied. It is also possible to utilize the method (5). When thefunctional group is an amino group, those steps of the method (3) or (4)which follow the conversion to an amino group can be applied.

As the method of converting the functional group (hydroxyl group) of (B)to a carboxyl group, there may be mentioned the methods based oncarboxymethyl etherification (e.g. the method comprising reacting theactive hydrogen-containing polymer (B) with a halogenated carboxylicacid (e.g. chloroacetic acid, chlorodifluoroacetic acid,3-chloropropionic acid, 3-chloro-2,2-difluoropropionic acid,4-chlorobutanoic acid, chloromethylbenzoic acid etc.) in the presence ofan alkali catalyst (e.g. sodium hydroxide, potassium hydroxide etc.),and the like method], the methods based on oxidation [e.g. the methodcomprising heating in an aqueous alkali solution in the presence ofpotassium permanganate or the like, the method based on air oxidationusing a platinum catalyst (e.g. platinum-activated carbon, platinumblack etc.) in the presence of a weakly basic compound (e.g. sodiumhydrogen carbonate, potassium carbonate etc.), the method comprisingheating under sulfuric acid-due acidic conditions in the presence of ahexavalent chromium compound or the like, and the like method], and thelike method. As the method of converting the carboxylic acid to an acidhalide, there may be mentioned the method comprising reacting with aphosphorus halide (e.g. phosphorus pentachloride etc.), the methodcomprising reacting with a thionyl halide (e.g. thionyl chloride etc.),and the like method. As the method of reacting the acid halide with anazide compound, there may be mentioned the method comprising mixing theacid halide and the azide compound (e.g. hydrazoic acid, sodium azideetc.) at a low temperature, and the like method; upon heating to 60 to150° C., the acid halide can be converted to an isocyanato group. As themethod of converting the carboxyl group to an amino group by reactionwith an azide compound, there may be mentioned the method comprisingreacting with a metal azide (e.g. sodium azide etc.) together withconcentrated sulfuric acid, the method comprising heating with diphenylphosphoroazidate, hydroxamic acid or hydroxylamine hydrochloride, andthe like method. As the method of converting the amino group to anisocyanato group, there may be mentioned the methods comprising reactingwith phosgene [e.g. the method comprising adding the amine dropwise to asolution of a phosgene species (e.g. phosgene, oxalyl chloride etc.),and the like method], the method comprising reacting withN,N′-carbonyldiimidazole, followed by decomposition at room temperature,the method comprising reacting with carbon monoxide in the presence of atransition metal complex catalyst (e.g. palladium chloride, rhodiumchloride, chloroplatinic acid etc.), the method comprising reacting withsodium hypochlorite, sodium hypobromite or the like, followed by alkalitreatment, and the like method. As the method of converting a secondaryhydroxyl group to a carbonyl group, there may be mentioned theoxidation-based methods [e.g. the method comprising heating in anaqueous alkali solution in the presence of potassium permanganate or thelike, the air oxidation method using a platinum catalyst (e.g.platinum-activated carbon, platinum black etc.), the method comprisingcarrying out the reaction under sulfuric acid-due acidic conditions inthe presence of a hexavalent chromium compound or the like and the likemethod], and the like method. As the method of converting a carbonylgroup to an amino group by reacting the carbonyl group with ammonia withsimultaneous reduction with hydrogen, there may be mentioned the methodcomprising carrying out the reaction in the presence of ammonia underpressurization with hydrogen gas in the presence of a hydrogenationcatalyst (e.g. Raney nickel, chloroplatinic acid etc.), and the likemethod. As the method of introducing an amino group into a hydroxylgroup, there may be mentioned the method comprising reacting thehydroxyl group with an ethylenimine (e.g. ethylenimine,N-methylethylenimine etc.), and the like method. As the isocyanatogroup-containing unsaturated compound, there may be mentionedisocyanatomethyl (meth)acrylate, isocyanatomethyl allyl ether and thelike.

The non-polyisocyanate-based polymer (NUP) preferably has a Mn of notlower than 500, more preferably not lower than 800, particularlypreferably not lower than 1,000, most preferably not lower than 1,200,and preferably not higher than 500,000, more preferably not higher than100,000, particularly preferably not higher than 10,000, most preferablynot higher than 5,000. Within such range, the adhesive strength (inparticular wet adhesive strength) becomes higher.

The use of an active hydrogen-containing polymer (B) terminally having afluorine atom-containing organic group among thenon-polyisocyanate-based polymer (NUP) species contributes to anincreased level of reactivity of the polymer, hence is preferred. Thus,the terminal structure after conversion to an isocyanato group ispreferably represented by —R_(f)—NCO (R_(f)being a perfluoroalkylenegroup containing 1 to 4 carbon atoms) and/or by —CH(CF₃)—NCO, morepreferably by —CH(CF₃)—NCO.

The alkali metal and alkaline earth metal content (in mmol/kg) in thepolymer of the invention is preferably 0 or lower than 0.04, morepreferably 0 or lower than 0.03, particularly preferably 0 or lower than0.02, most preferably 0 or lower than 0.01, based on the weight of thepolymer. Within such range, the storage stability of the polymer of theinvention becomes higher. The alkali metal and alkaline earth metalcontent in the polymer can be determined by subjecting a 30% (by weight)solution of the polymer in such a solvent as toluene, dimethylformamideor dimethyl sulfoxide, or an aqueous solution prepared by heating andincinerating 10 g of the polymer on a platinum dish and dissolving theash in 10 g of water, or a like pretreated sample to ion chromatographyor by titrating a solution prepared by dissolving 30 g of the polymer in100 ml of such a solvent as toluene, dimethylformamide or dimethylsulfoxide with {fraction (1/100)} N aqueous hydrochloric acid.

From the water-resistant adhesive strength viewpoint, theallophanate/biuret content (in % by weight) (AB content) in the polymerof the invention as expressed on the corresponding isocyanato groupcontent basis is preferably 0 or lower than 0.6, more preferably 0 orlower than 0.4, particularly preferably 0 or lower than 0.2, mostpreferably 0 or lower than 0.1, on the polymer weight basis. Within suchrange, the storage stability of the polymer of the invention becomeshigher.

In determining the AB content, 100 mg of the sample is added to 5 ml ofan anhydrous dimethylformamide solution containing di-n-butylamine (0.1%by weight) and naphthalene (0.1% by weight) and, after 40 minutes ofreaction at 70° C., 10 μl of acetic anhydride is added. After the lapseof 10 minutes, the reaction mixture is analyzed by gas chromatography,and the peak area ratio (SA) between di-n-butylacetamide and naphthaleneis determined. In a blank run, 100 mg of the sample is added to 5 ml ofan anhydrous dimethylformamide solution containing di-n-butylamine (0.1%by weight) and naphthalene (0.1% by weight) and, after 40 minutes ofreaction at 25° C., 10 ul of acetic anhydride is added. After the lapseof 10 minutes, the reaction mixture is analyzed by gas chromatography,and the peak area ratio (SB) between di-n-butylacetamide and naphthaleneis determined. The AB content is calculated as follows:AB content (% by weight)=[(SB−SA)/SB]×0.613  (1)

When the polymer of the invention is a tertiary amino group- and/orquaternary ammonio group-containing one, the number of these groupscontained therein (in number of groups/g) is preferably not smaller than1×10¹⁷, more preferably not smaller than 1×10¹⁸, most preferably notsmaller than 1×10¹⁹, and preferably not larger than 1×10²³, morepreferably not larger than 1×10²², most preferably not larger than1×10²¹, based on the polymer weight, from the reactivity of the polymerand the like viewpoint. The tertiary amino group- and/or quaternaryammonio group-containing polymer can be obtained by using a tertiaryamino group- and/or quaternary ammonio group-containing polyisocyanate(A) and/or active hydrogen-containing polymer (B) as the activehydrogen-containing polymer (B).

The polymer of the invention may optionally contain an activehydrogen-free and isocyanato group-free amine (C) in lieu of a tertiaryamino group and/or quaternary ammonio group in the polymer. When itcontains (C), the adhesive strength (in particular initial adhesivestrength) becomes better.

Employable as the active hydrogen-free, isocyanato group-free amine (C)are tertiary amines (C1), quaternary ammonium salts (C2), and the like.

As the tertiary amine (C1), there may be mentioned amines containing 1to 36 carbon atoms, including aliphatic amines, alicyclic amines,heterocyclic amines, aromatic ring-containing aliphatic amines, aromaticamines and the like. As the aliphatic amines, there may be mentionedaliphatic monoamines (trimethylamine, triethylamine, tripropylamine,trihexylamine, tridecylamine, N-methyldicyclohexylamine,N,N-dimethylcyclohexylamine,N-methyl-N,N-bis(3-dimethylaminopropyl)amine, N,N-dimethyleicosylamine,etc.), aliphatic polyamines [N,N,N-tris(3-dimethylaminopropyl)amine,tetraalkylalkylenediamines (N,N,N,N-tetramethylethylenediamine,N,N,N,N-tetraethylpropylenediamine, N,N,N,N-tetraethylundecylenediamine,etc.), polyalkylpolyalkylenepolyamines (pentamethyldiethylenetriamine,pentaethyldipropylenetriamine, hexamethyltriethylenetetramine,octamethylpentaethylenehexamine, etc.) etc.], and the like. As thealicyclic amines, there may be mentioned alicyclic monoamines(tricyclohexylamine, N,N-dimethylisophoronemonoamine,N,N-dimethyl-4-cyclohexylmethylcyclohexylamine,N,N-diethyl-4-dicyclohexylmethylcyclohexylamine, etc.), alicyclicpolyamines (tetramethyl-1,3-diaminocyclohexane etc.), and the like. Asthe heterocyclic amines, there may be mentioned heterocyclic monoamines(N-methylpiperidine, N-dimethylaminoethylpyridine, pyridine, quinoline,N-methylmorpholine, N-methyl-2,6-dimethylmorpholine, etc.), heterocyclicpolyamines [N,N′,N″-tris(dimethylaminopropyl)hexahydrotriazine,N,N′-dimethylpiperazine, 1,4-bis(dimethylaminoethyl)piperazine,pyridazine, pyrimidine, methylpurine, diazabicycloundecene,diazabicyclononene, bis(morpholinoethyl) ether, bis(morpholinopropyl)ether, bis(2,6-dimethylmorpholinoethyl) ether,1,2-bis(2,6-dimethylmorpholinoethoxy)ethane,bis(2,6-dimethylmorpholinoethoxyethyl) ether,2,2′-bis(2,6-dimethylmorpholinoethoxyethyl)diethyl ether, etc.], and thelike. As the aromatic ring-containing aliphatic amines, there may bementioned N,N-dimethylaminomethylbenzene, tetramethylxylylenediamine andthe like, and as the aromatic amines, there may be mentionedN,N-dimethylaniline, tetramethylphenylenediamine and the like.

Employable as the quaternary ammonium salts (C2) are those ones having astructure resulting from quaternization of the amino group(s) of (C1)with a quaternizing agent, and the like, and there may be mentionedaliphatic ammonium salts (tetramethylammonium carbonate etc.); alicyclicammonium salts (methyltricyclohexylammonium methyl sulfate etc.);heterocyclic ammonium salts (N,N-dimethylpiperidinium carbonate,N,N-dimethyl-2,6-dimethylmorpholinium carbonate, etc.); aromaticring-containing aliphatic ammonium salts(N,N,N-trimethylammoniummethylbenzene chloride etc.); aromatic ammoniumsalts (N,N,N-trimethylanilinium carbonate etc.); aliphatic polyammoniumsalts [hexaalkylalkylenediammonium salts(N,N,N,N′,N′,N′-hexamethylethylenediamine dicarbonate etc.),polyalkylpolyalkylenepolyammonium salts (heptamethyldiethylenetriaminetricarbonate) etc.]; alicyclic polyammonium salts(tetramethyl-1,3-diammoniumcyclohexane dichloride etc.); heterocyclicpolyammonium salts (N,N,N′,N′-tetramethylpiperazinium dicarbonate etc.);aromatic ring-containing aliphatic polyammonium salts(hexamethylxylylenediammonium dichloride etc.); aromatic polyammoniumsalts (hexamethylphenylenediammonium dichloride etc.); and the like.

Preferred among these are aliphatic amines, alicyclic amines,heterocyclic amines, and quaternary ammonium carbonate salts derivedfrom these. More preferred are aliphatic amines, heterocyclic amines,and quaternary ammonium carbonate salts derived from these. Particularlypreferred are heterocyclic polyamines. Most preferred are morpholinering-containing heterocyclic polyamines.

When the active hydrogen-free and isocyanato group-free amine (C) isused, the content (in % by weight) of (C) in the polymer of theinvention is preferably not lower than 0.05, more preferably not lowerthan 0.1, most preferably not lower than 0.5, and preferably not largerthan 20, more preferably not larger than 10, most preferably not largerthan 5, based on the weight of the polymer. Within such range, theadhesive strength (in particular initial adhesive strength) becomeshigher. The content of (C) in the polymer can be determined by treatingthe polymer with methanol or the like for reaction with the isocyanatogroups, followed by analysis by gas chromatography, liquidchromatography or the like. The method of incorporating (C) is notparticularly restricted. For example, the method comprising adding (C)to the polymer reaction apparatus before (including during) or afterpolymer synthesis, followed by mixing up, the method comprising adding(C) to the adhesive comprising the polymer of the invention just priorto use of the adhesive, followed by mixing up, or the like method.

Among the polymers of the invention, as the one having an epoxy group(e.g. glycidyl group, 2,3-oxacyclohexyl group etc.) as the reactivefunctional group, there may be mentioned one (EP) having at least oneepoxy group in each molecule, and the like. (EP) can be obtained byreacting the above-mentioned active hydrogen-containing polymer (B) withan epoxy group-containing compound, and by the like method. As the epoxygroup-containing compound, there may be mentioned epichlorohydrin,2,3-oxacyclohexyl chloride, allyl glycidyl ether, isocyanatoethylglycidyl ether and the like. Among them, epichlorohydrin and2,3-oxacyclohexyl chloride are preferred from the ease of reactionviewpoint, and epichlorohydrin is most preferred.

Among the polymers of the invention, as the one having a (meth)acryloylgroup as the reactive functional group, there may be mentioned one (MA)having at least one (meth)acryloyl group in each molecule, and the like.(MA) can be obtained by reacting the above-mentioned activehydrogen-containing polymer (B) with a (meth)acryloyl group-containingcompound, and by the like method. As the (meth)acryloyl group-containingcompound, there may be mentioned (meth)acrylic acid, (meth)acrylicchloride, glycidyl (meth)acrylate, isocyanatoethyl (meth)acrylate andthe like. Among these, (meth)acrylic acid and glycidyl (meth)acrylateare preferred from the ease of reaction viewpoint, and glycidyl(meth)acrylate is most preferred.

Among the polymers of the invention, as the one having acyano(meth)acryloyl group as the reactive functional group, there may bementioned one (CMA) having at least one cyano(meth)acryloyl group ineach molecule, and the like. (CMA) can be obtained by reacting theabove-mentioned active hydrogen-containing polymer (B) with acyano(meth)acryloyl group-containing compound, and by the like method.As the cyano(meth)acryloyl group-containing compound, there may bementioned cyano(meth)acrylic acid, cyano(meth)acrylic chloride, glycidylcyano(meth)acrylate, isocyanatocyanoethyl (meth)acrylate, and the like.Among these, cyano(meth)acrylic acid and glycidyl cyano(meth)acrylateare preferred from the ease of reaction viewpoint, and glycidylcyano(meth)acrylate is most preferred.

Among the polymers of the invention, as the one having an alkoxysilylgroup (e.g. trimethoxysilyl group, triethoxysilyl group etc.) as thereactive functional group, there may be mentioned one (AS) having atleast one alkoxysilyl group in each molecule, and the like. The polymer(AS) can be obtained by reacting the active hydrogen-containing polymer(B) mentioned above with an alkoxysilyl group-containing compound, andby the like method. As the alkoxysilyl group-containing compound, theremay be mentioned alkoxysilyl chlorides (trimethoxysilyl chloride,methyldimethoxysilyl chloride, triethoxysilyl chloride, etc.),alkoxysilyl glycidyl ethers (trimethoxysilyl glycidyl ether,methyldimethoxymethyl glycidyl ether, triethoxysilyl glycidyl ether,etc.), and the like. Among these, alkoxysilyl chlorides and alkoxysilylglycidyl ethers are preferred from the ease of reaction viewpoint, andalkoxysilyl glycidyl ethers are most preferred.

One or more other ingredients as necessary may further be incorporatedin the polymer of the invention. As the other ingredients, there may bementioned physiologically active medicinals (central nervous systemdrugs, antiallergic drugs, circulatory organ drugs, respiratory organdrugs, digestive organ drugs, hormones, metabolic drugs, carcinostaticdrugs, antibiotic preparations, chemotherapeutic agents, etc.), fillers(carbon black, red iron oxide, calcium silicate, sodium silicate,titanium oxide, acrylic resin powders, various ceramic powders, etc.),plasticizers (DBP, DOP, TCP, tributoxyethyl phosphate, various otheresters, etc.), stabilizers (trimethyldihydroquione,phenyl-p-naphthylamine, p-isopropoxydiphenylamine,diphenyl-p-phenylenediamine, etc.), and the like. When such aningredient or ingredients are incorporated, the level of addition (in %by weight) thereof is preferably not lower than 0.001, more preferablynot lower than 0.1, and preferably not larger than 20, more preferablynot larger than 5, based on the weight of the polymer of the invention.

A compound (D) having a polymerizable double bond with a cyano groupbound to either of the double bond-forming carbon atoms may beincorporated in the polymer of the invention for providing more rapidcurability. As such compound (D), there may be mentionedcyano(meth)acrylic 30 acid, methyl cyano(meth)acrylate,cyano(meth)acrylamide (Japanese Kokai Publication Hei-01-227762), andthe like.

When such a compound (D) is used, the usage (in % by weight) of (D) ispreferably not lower than 0.001, more preferably not lower than 0.1, andpreferably not larger than 50, more preferably not larger than 20, basedon the weight of the polymer.

In the presence of a trace amount of water or of moisture in the air,the polymer of the invention undergoes rapid polymerization to form afirm and strong film. Therefore, the other ingredient or ingredients tobe incorporated therein are required to be free of water/moisture. Whenput in a tightly closed vessel or container (e.g. ampoule etc.), thepolymer of the invention as produced can be stored for a long period.The storage temperature (in ° C.) is preferably not lower than −200,more preferably not lower than −100, most preferably not lower than 80,and preferably not higher than 100, more preferably not higher than 50,most preferably not higher than 30.

The polymer of the invention is suited for use in preventing fluidleakage from vital tissues and/or in adhesion of vital tissues, hence issuited for use as a medical adhesive. In particular, the polymer of theinvention provides a high level of water-resistant adhesive strengthand, therefore, can preferably be used in adhering vital tissues, suchas liver, kidney, spleen, pancreas, heart, lung, blood vessels (artery,vein, capillary vessel, etc.), trachea, bronchus, digestive tracts(esophagus, stomach, duodenum, small intestine, large intestine, rectum,etc.) and nerves, stopping bleeding, prevention of contents, enzyme,digestive juices or the like fluid from leaking from digestive organsand the like, temporary fixation prior to suture, reinforcing joints(sites of suture and sites of anastomosis) etc., and the like. Among thevital tissues, those tissues which are flexible and move actively, forexample lung, blood vessels, heart and the like tissue, are the suitabletargets of application of the polymer, and liver and lung are the bestsuited targets. The medical adhesive which comprises the polymer of theinvention is effective not only in adhering vital tissues but also inother fields of application, for example as a coating material foraneurysms/phlebeurysms and the like, as a sealing material, as aconglutination preventing agent for use on the occasion of surgical,operation, and the like. Furthermore, it can be effectively used injoining wound faces, incised wound faces and the like, and in adheringtreatment in dental surgery as well.

As for the method of adhering using the medical adhesive which comprisesthe polymer of the invention in surgical operations, there may bementioned the direct adhesion method comprising directly applying theadhesive to the site of cutting; the transfer adhesion method comprisingapplying the adhesive to a highly releasable film such as a siliconefilm or fluoroplastic film, covering the site of cutting with theadhesive together with the film and, after reaction, removing the film;the covering adhesion method comprising attaching a vital tissuesection, such as a vein, fascia or muscle, together with a cloth ornonwoven cloth made of Dacron, oxidized cellulose, collagen, chitin,polyurethane, polyester, PVA or the like, to the affected part andapplying the adhesive thereto; the suture fixation method comprisingstitching up a part of the vital tissue joint with a suture and applyingthe adhesive to the remaining part of the joint in the manner ofsealing; and the like method.

As for the method of application, there may be mentioned the methodusing a writing brush, tweezers, a spatula or the like, the spray methodusing Freon or nitrogen gas, and the like method.

BEST MODE FOR CARYYING OUT THE INVENTION

The following examples are further illustrative of the presentinvention. These examples are, however, by no means limitative of thescope of the invention. Unless otherwise specified, “part(s)” means“part(s) by weight”.

PRODUCTION EXAMPLE 1

An autoclave was charged with 15.5 parts of ethylene glycol and 3.8parts of potassium hydroxide and, after replacement with nitrogen, thecontents were dehydrated under vacuum at 120° C. for 60 minutes. Then, amixture of 784.5 parts of ethylene oxide and 200 parts of propyleneoxide was charged into the autoclave under pressure at 100 to 130° C.over about 10 hours. The reaction was allowed to proceed at 130° C.until the volatile matter content amounted to 0.1% or below. Thus wasobtained a crude polyether (c-EPRA) with an oxyethylene group content of80%.

PRODUCTION EXAMPLE 2

An autoclave was charged with 1,000 parts of the crude polyether(c-EPRA), the oxygen concentration in the gaseous phase was reduced to450 ppm by replacement with nitrogen, 30 parts of deionized water wasadded, 10 parts of synthetic magnesium silicate (sodium content: 0.2%)was then added, the oxygen concentration in the gaseous phase wasmaintained at 450 ppm by replacement with nitrogen, and the contentswere stirred at a stirring rate of 300 rpm at 90° C. for 45 minutes.Then, the reaction mixture was filtered through a glass filter (GF-75;product of Toyo Roshi Kaisha, Ltd.) under nitrogen to give an ethyleneoxide/propylene oxide random copolymer (EPRAl). The oxyethylene groupcontent of EPRAl was 80%, the alkali metal and/or alkaline earth metalcontent was 0.02 mmol/kg, and the Mn was 4,000.

PRODUCTION EXAMPLE 3

An autoclave was charged with 1,000 parts of the crude polyether(c-EPRA), and the oxygen concentration in the gaseous phase was reducedto 450 ppm by replacement with nitrogen. In a separate vessel, 30 partsof deionized water and 8 parts of synthetic magnesium silicate (sodiumcontent: 0.2%) were mixed up and deoxygenated, and the mixture was addedto the autoclave. The oxygen concentration in the gaseous phase wasmeasured and, after confirmation that it was 450 ppm, the contents werestirred at a stirring rate of 300 rpm at 90° C. for 90 minutes. Then,the reaction mixture was filtered through a glass filter (GF-75; productof Toyo Roshi Kaisha, Ltd.) under nitrogen to give an ethyleneoxide/propylene oxide random copolymer (EPRA2). The oxyethylene groupcontent of EPRA2 was 80%, the alkali metal and/or alkaline earth metalcontent was 0.04 mmol/kg, and the Mn was 4,000.

PRODUCTION EXAMPLE 4

An autoclave was charged with 1,000 parts of the crude polyether(c-EPRA), the oxygen concentration in the gaseous phase was reduced to450 ppm by replacement with nitrogen, 30 parts of deionized water wasadded, 12 parts of magnesium silicate (sodium content: 3% by weight) wasthen added, the oxygen concentration in the gaseous phase was adjustedto 450 ppm by replacement with nitrogen, and the contents were stirredat a stirring rate of 300 rpm at 90° C. for 240 minutes. Then, thereaction mixture was filtered through a glass filter (GF-75; product ofToyo Roshi Kaisha, Ltd.) under nitrogen to give an ethyleneoxide/propylene oxide random copolymer (EPRA3). The oxyethylene groupcontent of EPRA3 was 80%, the alkali metal and/or alkaline earth metalcontent was 0.08 mmol/kg, and the Mn was 4,000.

PRODUCTION EXAMPLE 5

An autoclave was charged with 320 parts of propylene glycol and 3.8parts of potassium hydroxide and, after replacement with nitrogen, thecontents were dehydrated under vacuum at 120° C. for 60 minutes. Then,680 parts of propylene oxide was charged into the autoclave underpressure at 100 to 130° C. over about 10 hours. The reaction as allowedto proceed at 130° C. until the volatile matter content amounted to 0.1%or below. Thus was obtained a crude polyether (c-PA).

PRODUCTION EXAMPLE 6

An autoclave was charged with 1,000 parts of the crude polyether (c-PA),the oxygen concentration in the gaseous phase was reduced to 450 ppm byreplacement with nitrogen, 30 parts of deionized water was added, 10parts of synthetic magnesium silicate (sodium content: 0.2%) was thenadded, the oxygen concentration in the gaseous phase was maintained at450 ppm by replacement with nitrogen, and the contents were stirred at astirring rate of 300 rpm at 90° C. for 45 minutes. Then, the reactionmixture was filtered through a glass filter (GF-75; product of ToyoRoshi Kaisha, Ltd.) under nitrogen to give a propylene oxide polymer(PAl). The oxyethylene group content of PAl was 0%, the alkali metaland/or alkaline earth metal content was 0.03 mmol/kg, and the Mn was200.

PRODUCTION EXAMPLE 7

An autoclave was charged with 1,000 parts of the crude polyether (c-PA),the oxygen concentration in the gaseous phase was reduced to 450 ppm byreplacement with nitrogen, 30 parts of deionized water was added, 12parts of magnesium silicate (sodium content: 3%) was then added, theoxygen concentration in the gaseous phase was maintained at 450 ppm byreplacement with nitrogen, and the contents were stirred at a stirringrate of 300 rpm at 90° C. for 240 minutes. Then, the reaction mixturewas filtered through a glass filter (GF-75; product of Toyo RoshiKaisha, Ltd.) under nitrogen to give a polypropylene glycol species(PA2). The oxyethylene group content of PA2 was 0%, the alkali metaland/or alkaline earth metal content was 0.08 mmol/kg, and the Mn was200.

PRODUCTION EXAMPLE 8

An autoclave was charged with 22.0 parts of dimethylaminoethylamine and,after replacement with nitrogen, a mixture of 400 parts of ethyleneoxide and 78 parts of propylene oxide was introduced under pressure at100 to 130° C. over about 3 hours. The reaction was allowed to proceedat 130° C. for 3 hours. To the reaction mixture was added 3.8 parts ofpotassium hydroxide and, after replacement with nitrogen, the contentswere dehydrated under vacuum at 120° C. for 60 minutes. Then, a mixtureof 400 parts of ethylene oxide and 100 parts of propylene oxide wascharged into the autoclave under pressure at 100 to 130° C. over about 7hours, and the reaction was allowed to proceed at 130° C. for 5 hours togive a crude polyether (c-3AEPRA). To this crude polyether (c-3AEPRA)was added 30 parts of deionized water, 10 parts of magnesium silicate(sodium content: 0.2% by weight) was then added, the oxygenconcentration in the gaseous phase was adjusted to 450 ppm or below byreplacement with nitrogen, and the contents were stirred at a stirringrate of 300 rpm at 90° C. for 45 minutes. Then, the reaction mixture wasfiltered through a glass filter (GF-75; product of Toyo Roshi Kaisha,Ltd.) under nitrogen to give a tertiary amino group-containing ethyleneoxide/propylene oxide random copolymer (3AEPRA). The oxyethylene groupcontent of 3AEPRA was 80%, the alkali metal and/or alkaline earth metalcontent was 0.02 mmol/kg, the tertiary amino group content was 3.0×10²⁰groups/g, and the Mn was 4,000.

PRODUCTION EXAMPLE 9

An autoclave was charged with 60.5 parts ofN,N,N′,N′-tetramethyethylenediammonium bisnitrate and, after replacementwith nitrogen, a mixture of 400 parts of ethylene oxide and 39.5 partsof propylene oxide was introduced under pressure at 100 to 130° C. overabout 3 hours. The reaction was allowed to proceed at 130° C. for 3hours. To the reaction mixture was added 3.8 parts of potassiumhydroxide and, after replacement with nitrogen, the contents weredehydrated under vacuum at 120° C. for 60 minutes. Then, a mixture of400 parts of ethylene oxide and 100 parts of propylene oxide was chargedinto the autoclave under pressure at 100 to 130° C. over about 7 hours,and the reaction was allowed to proceed at 130° C. for 5 hours to give acrude polyether (c-4AEPRA). The subsequent treatment was carried out inthe same manner as in Production Example 2 to give a quaternary ammoniogroup-containing ethylene oxide/propylene oxide random copolymer(4AEPRA). The oxyethylene group content of 4AEPRA was 80%, the alkalimetal and/or alkaline earth metal content was 0.02 mmol/kg, thequaternary ammonio group content was 3.1×10²⁰ groups/g, and the Mn was4,000.

PRODUCTION EXAMPLE 10

27.8 parts of epichlorohydrin and 2.22 parts of benzyltrimethylammoniumchloride were admixed with 1,112 parts of c-EPRA obtained in ProductionExample 1, and 58.9 parts of sodium hydroxide in granular form was addedover 5 hours while maintaining the temperature at 30° C. or below,followed by 3 hours of maturation at 30° C. The remainingepichlorohydrin was distilled off under reduced pressure, 33.4 parts ofdeionized water and 111 parts of magnesium silicate (sodium content:0.2% by weight) were then added, and the mixture was stirred at 90° C.for 45 minutes. Then, the reaction mixture was filtered through a glassfilter (GF-75; product of Toyo Roshi Kaisha, Ltd.) under nitrogen togive an epoxidized product (EP-EPRA). An autoclave after replacementwith nitrogen was charged with 800 parts of methanol and 20 parts oftriethylamine, a solution of 1,112 parts of EP-EPRA in 800 parts ofmethanol and 10 parts of hydrogen sulfide were charged with stirringthrough respective separate charging inlets while maintaining thereaction temperature at 25° C. and the pressure at 4 kg/cm². Aftercharging, the mixture was matured at that temperature for 3 hours, andthe residual hydrogen sulfide in the vessel was eliminated byintroducing into 30% aqueous sodium hydroxide by bubbling nitrogen intothe mixture. Furthermore, while bubbling nitrogen into the liquid, themethanol and triethylamine were distilled off at 100° C. and 20 mm Hgover 4 hours to give a mercapto group-containing ethyleneoxide/propylene oxide random copolymer (SEPRA). The oxyethylene groupcontent of SEPRA was 80%, the alkali metal and/or alkaline earth metalcontent was 0.02 mmol/kg, and the Mn was 4,000.

PRODUCTION EXAMPLE 11

A mercapto group-containing polypropylene glycol (SPA) was obtained inthe same manner as in Production Example 10 except that 55.6 parts ofc-PA obtained in Production Example 5 was used in lieu of 1,112 parts ofc-EPRA. The oxyethylene group content of SEPRA was 0%, the alkali metaland/or alkaline earth metal content was 0.03 mmol/kg, and the Mn was200.

PRODUCTION EXAMPLE 12

An autoclave was charged with 15.5 parts of ethylene glycol and 3.8parts of potassium hydroxide and, after replacement with nitrogen, amixture of 784.5 parts of ethylene oxide and 190 parts of propyleneoxide was introduced under pressure at 100 to 130° C. over about 10hours. The reaction was allowed to proceed at 130° C. for 8 hours, 10parts of 3,3,3-trifluoropropylene oxide was added under pressure, andthe reaction was allowed to proceed at 130° C. for 5 hours to give acrude fluorine-containing polyether (c-EPRFA). To 1,000 parts of thecrude polyether (c-EPRFA) was added 30 parts of deionized water,followed by addition of 10 parts of magnesium silicate (sodium content:0.2% by weight). After adjustment of the oxygen concentration in thegaseous phase to 450 ppm by replacement with nitrogen, the contents werestirred at a stirring rate of 300 rpm at 90° C. for 45 minutes. Then,the reaction mixture was filtered through a glass filter (GF-75; productof Toyo Roshi Kaisha, Ltd.) under nitrogen to give a fluorine-containingethylene oxide/propylene oxide random copolymer (EPRFA). The oxyethylenegroup content of EPRFA was 80%, the alkali metal and/or alkaline earthmetal content was 0.02 mmol/kg, and the Mn was 4,000.

PRODUCTION EXAMPLE 13

An autoclave was charged with 320 parts of propylene glycol and 3.8parts of potassium hydroxide and, after replacement with nitrogen, thecharge was dehydrated under vacuum at 120° C. for 60 minutes. Then, at100 to 130° C., 670 parts of propylene oxide was introduced underpressure over about 10 hours. The reaction was allowed to proceed at130° C. for 8 hours. Then, 10 parts of 3,3,3-trifluoropropylene oxidewas introduced under pressure, and the reaction was allowed to proceedat 130° C. for 5 hours to give a crude fluorine-containing polyether(c-PFA). The subsequent treatment was carried out in the same manner asin Production Example 12 to give a fluorine-containing polypropyleneglycol (PFA). The oxyethylene group content of PFA was 0%, the alkalimetal and/or alkaline earth metal content was 0.03 mmol/kg, and the Mnwas 200.

EXAMPLE 1

400 parts of (EPRAl) obtained in Production Example 2 was dehydratedunder reduced pressure at 90° C. for 8 hours, 93.6 parts ofOCN—CH₂(CF₂)₄CH₂—NCO (NCO group/OH group ratio: 3/1) was added at 25° C.and, after attaining homogeneity by stirring, the temperature was raisedto 80° C. over 30 minutes, and the reaction was allowed to proceed at80° C. for 8 hours to give a urethane prepolymer (UP1). During reaction,no abnormal viscosity increase was observed, and the NCO content of(UP1) was the same as the theoretical value.

EXAMPLE 2

A mixture of 124.1 parts of (EPRA1) obtained in Production Example 2 and13.8 parts of (PA2) obtained in Production Example 7 was dehydratedunder reduced pressure at 90° C., 42.4 parts of OCN—CH₂(CF₂)₂CH₂—NCO(NCO group/OH group ratio: 2/1) was then added at 25° C. and, afterattaining homogeneity by stirring, the temperature was raised to 80° C.over 30 minutes, and the reaction was allowed to proceed at 80° C. for 8hours to give a urethane prepolymer (UP2). During reaction, no abnormalviscosity increase was observed, and the NCO content of (UP2) was thesame as the theoretical value.

EXAMPLE 3

A mixture of 124.1 parts of (EPRA2) obtained in Production Example 3 and13.8 parts of (PA2) obtained in Production Example 7 was dehydratedunder reduced pressure at 90° C., 82.4 parts of OCN—CH₂(CF₂)₆CH₂—NCO(NCO group/OH group ratio: 2/1) was then added at 25° C. and, afterattaining homogeneity by stirring, the temperature was raised to 80° C.over 30 minutes, and the reaction was allowed to proceed at 80° C. for 8hours to give a urethane prepolymer (UP3). During reaction, no abnormalviscosity increase was observed, and the NCO content of (UP3) wasslightly lower than the theoretical value.

EXAMPLE 4

A mixture of 194.9 parts of (EPRA1) obtained in Production Example 2 and10.3 parts of (PA2) obtained in Production Example 7 was dehydratedunder reduced pressure at 90° C., 34.8 parts of tolylene diisocyanate(TDI) (NCO group/OH group ratio: 2/1) was then added at 25° C. and,after attaining homogeneity by stirring, the temperature was raised to80° C. over 30 minutes, and the reaction was allowed to proceed at 80°C. for 8 hours to give a urethane prepolymer (UP4).

EXAMPLE 5

The unreacted TDI was removed from (UP4) obtained in Example 4 byraising to 120° C. under reduced pressure and maintaining the reducedpressure (1 mm Hg) for 8 hours to give a urethane prepolymer (UP5).

EXAMPLE 6

100 parts of (UP4) obtained in Example 4 was heated to 80° C., 4.8 partsof (PA2) obtained in Production Example 7 was added dropwise theretoover 90 minutes, and the reaction was further allowed to proceed at 80°C. for 90 minutes to give a urethane prepolymer (UP6).

EXAMPLE 7

A mixture of 124.1 parts of (EPRAl) obtained in Production Example 2 and13.8 parts of (PA2) obtained in Production Example 7 was dehydratedunder reduced pressure at 90° C., 50.0 parts ofdiphenylmethanediisocyanate (MDI) (NCO group/OH group ratio: 2/1) wasthen added at 25° C. and, after attaining homogeneity by stirring, thetemperature was raised to 80° C. over 30 minutes, and the reaction wasallowed to proceed at 80° C. for 8 hours to give a urethane prepolymer(UP7).

EXAMPLE 8

The unreacted MDI was removed from (UP7) obtained in Example 7 byraising the temperature to 120° C. under reduced pressure andmaintaining the reduced pressure (1 mm Hg) for 12 hours while bubbling aminute amount of nitrogen through the liquid phase, to give a urethaneprepolymer (UP8).

EXAMPLE 9

A mixture of 194.9 parts of (3AEPRA) obtained in Production Example 8and 10.3 parts of (PA2) obtained in Production Example 7 was dehydratedunder reduced pressure at 90° C., 33.6 parts of hexamethylenediisocyanate (HDI) (NCO group/OH group ratio: 2/1) was then added at 25°C. and, after attaining homogeneity by stirring, the temperature wasraised to 80° C. over 30 minutes, and the reaction was allowed toproceed at 80° C. for 8 hours to give a urethane prepolymer (UP9)

EXAMPLE 10

A urethane prepolymer (UP10) was obtained in the same manner as inExample 9 except that 44.4 parts of isophoronediisocyanate (IPDI) wasused in lieu of 33.6 parts of hexamethylene diisocyanate (HDI).

EXAMPLE 11

A urethane prepolymer (UP11) was obtained in the same manner as inExample 9 except that (4AEPRA) obtained in Production Example 9 was usedin lieu of (3AEPRA).

EXAMPLE 12

A urethane prepolymer (UP12) was obtained in the same manner as inExample 9 except that a mixture of 97.5 parts of (EPRA3) obtained inProduction Example 4 and 97.4 parts of (EPRAL) obtained in ProductionExample 2 was used in lieu of (3AEPRA).

EXAMPLE 13

A mixture of 194.9 parts of (EPRA1) obtained in Production Example 2 and10.3 parts of (PA2) obtained in Production Example 7 was dehydratedunder reduced pressure at 90° C., 33.6 parts of hexamethylenediisocyanate (HDI) (NCO group/OH group ratio: 2/1) was then added at 25°C. and, after attaining homogeneity by stirring, the temperature wasraised to 80° C. over 30 minutes, and the reaction was allowed toproceed at 80° C. for 14 hours to give a urethane prepolymer (UP13).

EXAMPLE 14

A urethane prepolymer (14) was obtained by mixing up 100 parts by weightof (UP13) obtained in Example 13 and 0.6 parts by weight ofdiazabicycloundecene.

EXAMPLE 15

A urethane prepolymer (15) was obtained by mixing up 100 parts by weightof (UP13) obtained in Example 13 and 5 parts by weight ofbis(2,6-dimethylmorpholinoethyl) ether.

EXAMPLE 16

A urethane prepolymer (16) was obtained by mixing up 100 parts by weightof (UP13) obtained in Example 13 and 0.6 parts by weight ofN,N′,N″-tris(dimethylaminopropyl)hexahydrotriazine.

EXAMPLE 17

A urethane prepolymer (17) was obtained by mixing up 100 parts by weightof (UP13) obtained in Example 13 and 2 parts by weight ofN,N,N′,N′-tetramethylpiperazinium dicarbonate.

EXAMPLE 18

A urethane prepolymer (UP18) was obtained in the same manner as inExample 13 except that 44.4 parts of isophoronediisocyanate (IPDI) wasused in lieu of 33.6 parts of hexamethylene diisocyanate (HDI).

EXAMPLE 19

A urethane prepolymer (19) was obtained by mixing up 100 parts by weightof (UP18) obtained in Example 18 and 0.6 parts by weight ofdiazabicycloundecene.

EXAMPLE 20

400 parts of (SEPRA) obtained in Production Example 10 was dehydratedunder reduced pressure at 90° C. for 8 hours, 93.6 parts ofOCN—CH₂(CF₂)₄CH₂—NCO (NCO group/OH group ratio: 3/1) was added at 25° C.and, after attaining homogeneity by stirring, the temperature was raisedto 80° C. over 30 minutes, and the reaction was allowed to proceed at80° C. for 8 hours to give a urethane prepolymer (UP20).

EXAMPLE 21

A mixture of 124.1 parts of (SEPRA) obtained in Production Example 10and 13.8 parts of (SPA) obtained in Production Example 11 was dehydratedunder reduced pressure at 90° C. for 8 hours, 62.4 parts ofOCN—CH₂(CF₂)₄CH₂—NCO (NCO group/OH group ratio: 2/1) was then added at25° C. and, after attaining homogeneity by stirring, the temperature wasraised to 80° C. over 30 minutes, and the reaction was allowed toproceed at 80° C. for 8 hours to give a urethane prepolymer (UP21).

EXAMPLE 22

10 parts of platinum black was added to 100 parts of (EPRFA) obtained inProduction Example 12, and the reaction was allowed to proceed at 60° C.with stirring for 10 hours while passing air through the gaseous phase.The reaction mixture was filtered through a glass filter (GF-75; productof Toyo Roshi Kaisha, Ltd.) to give a polyether having carbonyl groupsintroduced therein. Then, 10 parts of ammonia was introduced underpressure, the reaction was allowed to proceed at 25° C. for 2 hours, 1part of Raney nickel was then added, and the reaction system waspressurized to 90 atm with hydrogen gas at 25° C. The temperature wasgradually raised, and the reaction was allowed to proceed at 40° C. for5 hours and then at 70° C. for 5 hours. The excess ammonia, hydrogen andthe byproduct water were removed under reduced pressure, and theremaining reaction mixture was filtered through a glass filter (GF-75;product of Toyo Roshi Kaisha, Ltd.) to give a polyether having aminogroups introduced therein. To this was added 0.5 parts of palladiumchloride and, while passing carbon monoxide through the mixture, thereaction was allowed to proceed at 65° C. for 3 days. The excess carbonmonoxide was removed under reduced pressure, and the reaction mixturewas filtered through a glass filter (GF-75; product of Toyo RoshiKaisha, Ltd.) to give a polymer (NUPL) resulting from conversion of theterminal functional groups to isocyanato groups.

EXAMPLE 23

The procedure of Example 22 was followed in the same manner except thata mixture of 95 parts of the random copolymer (EPRFA) obtained inProduction Example 12 and 5 parts of (PFA) obtained in ProductionExample 13 was used in lieu of 100 parts of (EPRFA), to give a polymer(NUP2) resulting from conversion of the terminal functional groups toisocyanato groups.

COMPARATIVE EXAMPLE 1

400 parts of (EPRA3) obtained in Production Example 4 was dehydratedunder reduced pressure at 90° C., 93.6 parts of OCN—CH₂(CF₂)₄CH₂—NCO(NCO group/OH group ratio: 3/1) was then added at 25° C. and, afterattaining homogeneity by stirring, the temperature was raised to 80° C.over 30 minutes, and the reaction was allowed to proceed at 80° C. for 8hours to give a comparative urethane prepolymer (HUP1).

COMPARATIVE EXAMPLE 2

A mixture of 124.1 parts of (EPRA3) obtained in Production Example 4 and13.8 parts of (PA2) obtained in Production Example 7 (the alkali metaland alkaline earth metal content in the mixture: 0.08 mmol/kg) wasdehydrated under reduced pressure at 90° C., 82.4 parts ofOCN—CH₂(CF₂)₆CH₂—NCO (NCO group/OH group ratio: 2/1) was then added at25° C. and, after attaining homogeneity by stirring, the temperature wasraised to 80° C. over 30 minutes, and the reaction was allowed toproceed at 80° C. for 8 hours to give a comparative urethane prepolymer(HUP2).

COMPARATIVE EXAMPLE 3

A mixture of 2.2 parts of (EPRAL) obtained in Production Example 2 and19.9 parts of (PA1) obtained in Production Example 6 was dehydratedunder reduced pressure at 90° C., 82.4 parts of OCN—CH₂(CF₂)₆CH₂—NCO(NCO group/OH group ratio: 2/1) was then added at 25° C. and, afterattaining homogeneity by stirring, the temperature was raised to 80° C.over 30 minutes, and the reaction was allowed to proceed at 80° C. for 8hours to give a comparative urethane prepolymer (HUP3).

COMPARATIVE EXAMPLE 4

A comparative urethane prepolymer (HUP4) was obtained in the same manneras in Comparative Example 3 except that 20.0 parts of (PA1) was used inlieu of the mixture of 2.2 parts of (EPRA1) and 19.9 parts of (PA1).

Each polymer was evaluated for the following items, and the results thusobtained are shown in Table 1 and Table 2.

<Viscosity>

Viscosity measurements were made using a DA viscometer according to themethod D prescribed in JIS K 7117-1987.

<Saturated Water Absorption>

Using an apparatus for D/W method of testing for water absorption rates(buret capacity: 25 ml, length: 55 cm, testing solution: physiologicalsaline, small opening diameter: 2 mm) as shown in JIS K 7224-1996-Illustration 1, measurements were carried out in a room maintained at25° C. and 50% humidity with Whatman's glass microfiber filter GF/Ahaving a diameter of 3.7 cm installed in lieu of the nonwoven fabric,together with a polycarbonate cylinder having an inside diameter of 3.7cm, and the water absorption 30 minutes after setting of 1.0 g of eachpolymer was read.

<Initial Water Absorption Rate>

In the same manner as in the saturated water absorption measurement, thewater absorption 2 minutes after setting was measured and the value wasmultiplied by 1/2.

<Wet Elongation Percentage>

Test specimens prepared by applying the polymer onto a glass plate to asize of 10 cm square and a thickness of about 100 um using anapplicator, allowing the coating to stand at 25° C. and 50% RH for 48hours for attaining curing, allowing the same to stand in aphysiological saline bath at 25° C. and, after 24 hours, taking out thesame, and stamping out of the same using a No. 3 dumbbell-shaped diedescribed in JIS K 6251-1993 were kept in physiological saline for 1hour, deprived of moisture with gauze, precisely measured for thicknessand, within 5 minutes, tested for elongation at break at a rate ofpulling of 300 mm/min in an atmosphere of 25° C. and 50% RH according toJIS K 6251-1993. The tensile testing machine used was Shimadzu Corp'smodel AGS-500B autograph.

<Wet 100% Modulus>

Simultaneously with the wet elongation percentage measurements, thetension corresponding to 100% elongation was measured, and the wet 100%modulus was calculated by dividing that value by the sectional area ofthe test specimen.

<Oxyethylene Group Content>

The content was calculated based on ¹H—NMR data.

<Isocyanato Group Content>

The polymer was dissolved in a toluene solution of dibutylamine with aconcentration of 0.5 M and, after 30 minutes of stirring, titration wascarried out with ½ N hydrochloric acid in methanol. The thus-foundnumber of moles of NCO groups per unit weight was multiplied by 42.

<Allophanate/biuret Content Expressed in Terms of Isocyanato GroupContent>

The sample (100 mg) was added to 5 ml of an anhydrous dimethylformamidesolution containing 0.1% by weight of di-n-butylamine and 0.1% by weightof naphthalene and, after 40 minutes of reaction at 70° C., 10 μl ofacetic anhydride was added. After the lapse of 10 minutes, the reactionmixture was analyzed by gas chromatography, and the peak area ratio (SA)between di-n-butylacetamide and naphthalene was determined. In a blankrun, 100 mg of the sample was added to 5 ml of an anhydrousdimethylformamide solution containing 0.1% by weight of di-n-butylamineand 0.1% by weight of naphthalene and, after 40 minutes of reaction at25° C., 10 pl of acetic anhydride was added. After the lapse of 10minutes, the reaction mixture was analyzed by gas chromatography, andthe peak area ratio (SB) between di-n-butylacetamide and naphthalene wasdetermined. The content in question was calculated as follows:[(SB—SA)/SB]×0.613.

<Alkali Metal and Alkaline Earth Metal Content>

The sample (10 g) was heated and incinerated on a platinum dish, the ashwas dissolved in 10 g of water, the solution was subjected to ionchromatography, and the content in question was determined.

<Mn>

The Mn was determined by GPC using polyethylene glycol species asstandard substances.

<Content of Isocyanato Group-containing Polymer Molecules Having aMolecular Weight of 500 to 500,000>

The content was calculated based on the molecular weight distributioncurve obtained by GPC, using a refractive index detector, of a solutionof the polymer in a dimethylformamide solution of dibutylamine (standardsubstances: polyethylene glycol species) and the molecular weightdistribution curve for urethane prepolymer molecules having a Mn of notlower than 500 but not higher than 500,000 as obtained by GPC, using anultraviolet detector, of a solution of the polymer in adimethylformamide solution of 4-aminopyridine (standard substances:N-methylaminopyridine-ethylene oxide adducts).

<Number of Tertiary Amino Group and/or Quaternary Ammonio GroupContented>

The number was calculated based on ¹H-NMR data.

<Content of Amine (C)>

The polymer was dispersed in methanol, the dispersion was stirred atroom temperature for 1 hour, the solution fraction was analyzed by gaschromatography, and the content was calculated.

<Adhesive Appearance>

1 g of the polymer was placed in a 10-mL screw tube, and the fluidityand homogeneity at 25° C. were evaluated according to the followingcriteria:

-   -   Excellent: Fluid and homogeneous;    -   Fair: Rather poorly fluid but homogeneous;    -   Poor: Poorly fluid and lumps are observed here and there.        <Applicability>

Two collagen films (1×5 cm) were immersed in physiological saline for 24hours, the surface water was then wiped off, and about 0.1 mL of thepolymer was applied to the terminal 1×1 cm area of one of the filmsusing a spatula made of polytetrafluoroethylene. The applicability onthat occasion was evaluated according to the following criteria:

-   -   Excellent: Readily spreadable, hence good workability;    -   Poor: Hardly spreadable, hence poor workability.        <Initial Adhesive Strength>

Two collagen films (1×5 cm) were immersed in physiological saline for 24hours, the surface water was then wiped off, and about 0.1 mL of thepolymer was applied to the terminal 1×1 cm area of one of the filmsusing a spatula made of polytetrafluoroethylene, and the terminal 1×1 cmarea of the other film was put on top of the coated area. for adheringto give a test specimen. A weight of 100 g was placed on the adheredarea (1×1 cm) of this test specimen, the whole was allowed to stand inan atmosphere of 37° C. and 98% humidity for 5 minutes, the weight wasthen removed, and the tensile strength was measured in an atmosphere of37° C. and 98% humidity according to JIS K 6850-1999. The load at breakwas recorded as the initial adhesive strength. The tensile testingmachine used was a Shimadzu Corp's model AGS-500B autograph, and therate of pulling was 300 mm/min.

<Water-resistant Adhesive Strength>

Two collagen films (1×5 cm) were immersed in physiological saline for 24hours, the surface water was then wiped off, and about 0.1 mL of thepolymer was applied to the terminal 1×1 cm area of one of the filmsusing a spatula made of polytetrafluoroethylene, and the terminal 1×1 cmarea of the other film was put on top of the coated area for adhering togive a test specimen. A weight of 100 g was placed on the adhered area(1×1 cm) of this test specimen, and the whole was allowed to stand at37° C. for 30 minutes. The weight was then removed, and the testspecimen, after 48 hours of immersion in physiological saline, wasmeasured for tensile strength in an atmosphere of 37° C. and 98%humidity according to JIS K 6850-1999. The load at break was recorded asthe adhesive strength. The tensile testing machine used was a ShimadzuCorp's model AGS-500B autograph, and the rate of pulling was 300 mm/min.

<Repeated Bending Adhesive Strength>

Two collagen films (1×5 cm) were immersed in physiological saline for 24hours, the surface water was then wiped off, and about 0.1 mL of thepolymer was applied to the terminal 1×1 cm area of one of the filmsusing a spatula made of polytetrafluoroethylene, and the terminal 1×1 cmarea of the other film was put on top of the coated area for adhering togive a test specimen. A weight of 100 g was placed on the adhered area(1×1 cm) of this test specimen, and the whole was allowed to stand at37° C. for 30 minutes. The weight was then removed, the specimen wasmounted, with both ends of the adhered area fixed, on a bending testingmachine placed in an atmosphere of 37° C. and 95% relative humidity insuch a manner that the middle of the adhered area (1×1 cm) might bebent, and bending was repeated for one week under the followingconditions: bending frequency: once/minute, bending angle: 90/2700. Thetensile strength of the thus repeatedly bent test specimen was measuredin an atmosphere of 37° C. and 98% humidity according to JIS K6850-1999. The load at break was recorded as the adhesive strength. Thetensile testing machine used was Shimadzu Corp's model AGS-500Bautograph, and the rate of pulling was 300 mm/min. TABLE 1 Example 1 2 34 5 6 7 Polymer UP1 UP2 UP3 UP4 UP5 UP6 UP7 Viscosity(Pa · s) 11.0 10.290.1 10.5 12.1 14.4 11.4 Saturated water absorption 0.60 0.65 0.45 0.500.60 0.60 0.50 (g/g) Initial water absorption rate 0.05 0.06 0.03 0.060.05 0.05 0.07 (g/g · min) Wet elongation percentage 600 800 300 400 600600 400 (%) Wet 100% modulus (MPa) 0.55 0.60 0.80 0.35 0.65 0.60 0.30Oxyethylene group content 65 55 45 65 66 64 53 (wt %) NCO content*¹ (wt%) 3.4 4.7 3.7 3.5 3.1 1.3 4.6 Metal content*³ (mmol/kg) 0.016 0.0200.028 0.020 0.020 0.019 0.019 AB content*² (wt %) 0.06 0.07 0.15 0.060.06 0.06 0.07 Polymer content*⁴ (wt %) 98.0 98.5 98.5 97.0 99.5 98.597.2 Amino content*⁶ (groups/g) <0.01 <0.01 <0.01 <0.01 <0.01 <0.01<0.01 Amine content (wt %) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Adhesiveappearance Excellent Excellent Excellent Excellent Excellent ExcellentExcellent Applicability Excellent Excellent Fair Excellent ExcellentExcellent Excellent Initial adhesive strength 1.1 1.0 0.6 0.4 1.0 1.10.4 Water-resistant adhesive 0.9 1.5 0.8 0.6 1.5 1.4 0.6 strengthRepeated bending adhesive 0.9 0.8 0.5 0.2 1.0 1.1 0.3 strength Example 89 10 11 12 13 14 Polymer UP8 UP9 UP10 UP11 UP12 UP13 UP14 Viscosity(Pa ·s) 17.0 15.1 16.1 14.7 15.3 8.4 8.3 Saturated water absorption 0.60 0.600.60 0.65 0.70 0.50 0.60 (g/g) Initial water absorption rate 0.05 0.050.05 0.06 0.05 0.04 0.06 (g/g · min) Wet elongation percentage 600 800700 800 800 900 700 (%) Wet 100% modulus (MPa) 0.55 0.55 0.60 0.65 0.650.35 0.45 Oxyethylene group content 52 65 62 65 65 65 65 (wt %) NCOcontent*¹ (wt %) 4.2 3.5 3.3 3.4 3.5 3.5 3.5 Metal content*³ (mmol/kg)0.019 0.020 0.019 0.020 0.020 0.020 0.020 AB content*² (wt %) 0.07 0.060.06 0.07 0.07 0.06 0.06 Polymer content*⁴ (wt %) 98.5 98.5 98.5 98.598.5 97.0 97.0 Amino content*⁶ (groups/g) <0.01 2.4 × 10₂₀ 2.3 × 10₂₀2.5 × 10₂₀ 1.2 × 10₂₀ <0.01 <0.01 Amine content (wt %) <0.1 <0.1 <0.1<0.1 <0.1 <0.1 0.6 Adhesive appearance Excellent Excellent ExcellentExcellent Excellent Excellent Excellent Applicability ExcellentExcellent Excellent Excellent Excellent Excellent Excellent Initialadhesive strength 1.0 1.2 1.1 1.1 0.8 0.3 1.1 Water-resistant adhesive1.4 1.5 0.9 1.2 1.2 0.6 0.9 strength Repeated bending adhesive 1.2 1.00.9 0.8 0.6 0.2 0.9 strength

TABLE 2 Example 15 16 17 18 19 20 21 Polymer UP15 UP16 UP17 UP18 UP19UP20 UP21 Viscosity (Pa · s) 7.0 8.3 7.4 9.3 9.5 11.1 10.5 Saturatedwater absorption 0.60 0.60 0.60 0.50 0.60 0.50 0.55 (g/g) Initial waterabsorption rate 0.06 0.06 0.06 0.04 0.06 0.05 0.05 (g/g · min) Wetelongation percentage 700 700 800 900 700 800 600 (%) Wet 100% modulus(MPa) 0.45 0.50 0.45 0.35 0.45 0.55 0.55 Oxyethylene group content 65 6565 63 63 65 50 (wt %) NCO content*¹ (wt %) 3.5 3.5 3.5 3.3 3.3 3.4 4.2Metal content*³ (mmol/kg) 0.019 0.020 0.019 0.019 0.019 0.016 0.014 ABcontent*² (wt %) 0.06 0.06 0.06 0.05 0.05 0.06 0.05 Polymer content*⁴(wt %) 97.0 97.0 97.0 97.0 97.0 98.0 98.0 Amino content*⁵ (groups/g)<0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 Amine content (wt %) 4.8 0.62.0 <0.1 <0.1 <0.01 <0.01 Adhesive appearance Excellent ExcellentExcellent Excellent Excellent Excellent Excellent ApplicabilityExcellent Excellent Excellent Excellent Excellent Excellent ExcellentInitial adhesive strength 1.2 1.1 0.8 0.3 1.2 1.5 1.4 Water-resistentadhesive 1.0 0.9 0.8 0.6 1.2 1.4 1.3 strength Repeated bending adhesive1.0 0.8 0.6 0.2 0.9 1.3 1.0 strength Example Comparative Example 22 23 12 3 4 Polymer NUP1 NUP2 HUP1 HUP2 HUP3 HUP4 Viscosity (Pa · s) 6.4 3.12510 2840 5.3 2.7 Saturated water absorption 0.60 0.55 0.40 0.40 0.150.10 (g/g) Initial water absorption rate 0.05 0.05 0.02 0.02 0.02 0.01(g/g · min) Wet elongation percentage 700 600 200 300 150 100 (%) Wet100% modulus (MPa) 0.60 0.55 0.80 0.75 0.70 0.80 Oxyethylene groupcontent 78 73 65 45 8 <0.1 (wt %) NCO content*¹ (wt %) 2.1 3.2 2.8 3.18.0 8.2 Metal content*³ (mmol/kg) 0.020 0.020 0.065 0.050 0.006 0.006 ABcontent*² (wt %) <0.01 <0.01 0.64 0.70 0.12 0.14 Polymer content*⁴ (wt%) 99.5 99.5 98.0 98.0 99.0 99.0 Amino content*⁵ (groups/g) <0.01 <0.01<0.01 <0.01 <0.01 <0.01 Amine content (wt %) <0.01 <0.01 <0.1 <0.01<0.01 <0.01 Adhesive appearance Excellent Excellent Poor Poor ExcellentExcellent Applicability Excellent Excellent Poor Poor Fair Fair Initialadhesive strength 1.2 1.2 0.2 0.2 <0.1 <0.1 Water-resistent adhesive 1.01.1 0.3 0.5 0.2 0.1 strength Repeated bending adhesive 1.4 1.2 <0.1 <0.1<0.1 <0.1 strength*¹Isocyanato group content*²Allophanate/biuret content expressed in terms of isocyanato groupcontent*³Alkali metal and alkaline earth metal content*⁴Content of molecules of Mn (500 to 500,000)*⁵Number of tertiary amino groups and/or quaternary ammonio groupscontained.

The following evaluation test was carried out using (UP1) to (UP3), HUP1and HUP2. The results are shown in Table 3.

<In Vivo Adhesion Test>

The carotid artery (outside diameter about 4 mm) of an adult goat wastemporarily ligated over a length of about 5 mm by means of two vascularclamps and the blood vessel portion between them was given an incisionabout 3 mm in length in the longitudinal direction of the vessel, and0.1 mL of the polymer of the invention was applied onto the incisionusing a spatula made of polytetrafluoroethylene. Five minutes later, theblood flow was resumed by removing the two vascular clamps and, further5 minutes later, the occurrence or nonoccurrence of bleeding was judgedby visual observation to evaluate the adhesive properties of thepolymer. TABLE 3 Polymer Evaluation result Example1 U P 1 No bleedingExample2 U P 2 No bleeding Example3 U P 3 No bleeding Comparative H U P1 Bleeding from around Example1 Comparative H U P 2 Bleeding from aroundExample2

Industrial Aplicability

The polymer of the invention is very good in appearance, water-resistantadhesive strength, repeated bending adhesive strength, applicability andinitial adhesive strength. Therefore, it is suitable for use in adheringvital tissues, and the like, and thus is best suited for use as amedical adhesive in adhering vital tissues, such as liver, kidney,spleen, pancreas, heart, lung, blood vessels (artery, vein, capillaryvessel, etc.), trachea, bronchus, digestive tracts (esophagus, stomach,duodenum, small intestine, large intestine, rectum, etc.) and nerves, instopping bleeding, in preventing contents, enzyme, digestive juices orthe like fluid from leaking from digestive organs, temporary fixationprior to suture, reinforcing joints (sites of suture and sites ofanastomosis) etc., and the like. Furthermore, it exhibits highreliability and high performance characteristics in joining wound faces,incised wound faces and the like, and in adhering treatment in dentalsurgery as well.

1. An isocyanato group-containing polymer capable of forming a curedfilm and useful as a medical adhesive, which has a viscosity at 37° C.of 0.5 to 2,000 Pa·s, shows a saturated water absorption of 0.2 to 5ml/g, and has the alkali metal and alkaline earth metal content of 0(zero) or lower than 0.04 mmol/kg based on the weight of the polymer. 2.The polymer according to claim 1, which shows an initial waterabsorption rate of 0.01 to 0.5 ml/g·min, the wet elongation percentageof the cured film of 100 to 1,500% and the wet 100% modulus of the curedfilm of 0.01 to 10 MPa, and contains oxyethylene groups and, in whichthe oxyethylene group content is 30 to 100% by weight based on theweight of the polymer.
 3. (Canceled)
 4. (Canceled)
 5. (Canceled) 6.(Canceled)
 7. The polymer according to claim 1, wherein the isocyanatogroup content is 0.1 to 20% by weight based on the weight of thepolymer.
 8. The polymer according to claim 1, wherein theallophanate/biuret content expressed as the corresponding isocyanatogroup content is 0 or lower than 0.6% by weight based on the weight ofthe polymer.
 9. (Canceled)
 10. The polymer according to claim 1, whereinthe content of isocyanato group-containing polymer molecules having anumber average molecular weight of 500 to 500,000 is 98 to 100% byweight based on the weight of the polymer.
 11. The polymer according toclaim 1, which is a tertiary amino group- and/or quaternary ammoniogroup-containing one and, in which the number of the tertiary aminogroups and quaternary ammonio groups contained therein is 1×10¹⁷ to1×10²³ groups/g based on the weight of the polymer
 12. The polymeraccording to claim 1, which contains an active hydrogen-free andisocyanato group-free amine (C).
 13. The polymer according to claim 1,which comprises an isocyanato group-containing polymer derived from apolyisocyanate (A) and an active hydrogen-containing polymer (B)selected from the group consisting of hydroxyl group-containingpolyethers (B1), mercapto group-containing polyethers (B2), primaryand/or secondary amino group-containing polyethers (B3), carboxylgroup-containing polyethers (B4), hydroxyl group-containing polyesters(B5), mercapto group-containing poly(thio)esters (B6), primary and/orsecondary amino group-containing polyesters (B7), carboxylgroup-containing polyesters (B8), hydroxyl group-containing polyamides(B9), mercapto group-containing polyamides (B10), primary and/orsecondary amino group-containing polyamides (B11) and carboxylgroup-containing polyamides (B12).
 14. The polymer according to claim13, wherein the polyisocyanate (A) comprises a fluorine-containingaliphatic polyisocyanate and/or a fluorine-containing alicyclicpolyisocyanate.
 15. The polymer according to claim 13, wherein thealkali metal and/or alkaline earth metal content in the activehydrogen-containing polymer (B) is 0 (zero) or lower than 0.07 mmol/kgbased on the weight of (B).
 16. The polymer according to any one ofclaims 13, wherein the active hydrogen-containing polymer (B) is anethylene oxide-propylene oxide random copolymer.
 17. An isocyanatogroup-containing polymer polymer capable of forming a cured film anduseful as a medical adhesive, which has a viscosity at 37° C. of 0.5 to2,000 Pa·s, shows a saturated water absorption of 0.2 to 5 ml/g, and hasa structure resulting from conversion of at least one functional groupin an active hydrogen-containing polymer (B) selected from the groupconsisting of polyethers, polyesters and polyamides to an isocyanatogroup.
 18. The polymer according to claim 1, which is intended for usein preventing fluid leakage from a vital tissue and/or adhering a vitaltissue.
 19. The polymer according to claim 18, wherein the vital tissuecomprises at least one tissue selected from the group consisting ofliver, kidney, spleen, pancreas, heart, lung, blood vessels, trachea,bronchus, digestive tracts and nerves.
 20. A process for producing thepolymer according to claim 1, which comprises converting an activehydrogen-containing polymer (B) having an alkali metal and/or alkalineearth metal content of 0 (zero) or lower than 0.07 mmol/kg to anisocyanato group-containing polymer.
 21. An isocyanato group-containingpolymer capable of forming a cured film and useful as a medicaladhesive, wherein the content of isocyanato group-containing polymermolecules having a number average molecular weight of 500 to 500,000 is98 to 100% by weight based on the weight of the polymer.
 22. Anisocyanato group-containing polymer capable of forming a cured film anduseful as a medical adhesive, which is obtainable by using a tertiaryamino group- and/or quaternary ammonio group-containing polyisocyanate,and is a tertiary amino group- and/or quaternary ammoniogroup-containing polymer and, in which the number of the tertiary aminogroups and quaternary ammonio groups contained therein is 1×10¹⁷ to1×10²³ groups/g based on the weight of the polymer.
 23. An isocyanatogroup-containing polymer capable of forming a cured film and useful as amedical adhesive, which comprises an isocyanato group-containing polymerderived from a polyisocyanate (A) and an active hydrogen-containingpolymer (B) selected from the group consisting of mercaptogroup-containing polyethers (B2), primary and/or secondary aminogroup-containing polyethers (B3), carboxyl group-containing polyethers(B4), hydroxyl group-containing polyesters (B5), mercaptogroup-containing poly(thio)esters (B6), primary and/or secondary aminogroup-containing polyesters (B7), carboxyl group-containing polyesters(B8), hydroxyl group-containing polyamides (B9), mercaptogroup-containing polyamides (B10), primary and/or secondary aminogroup-containing polyamides (B11) and carboxyl group-containingpolyamides (B12).
 24. The polymer according to claim 17, which isintended for use in preventing fluid leakage from a vital tissue and/oradhering a vital tissue.